Oxime ester photoinitiators

ABSTRACT

Oxime ester compounds of the formula I, II, III, IV or V, wherein Z is for example (formula A); Z 1  for is NO 2 , unsubstituted or substituted C 7 -C 20 aroyl or unsubstituted or substituted C 4 -C 20 heteroaroyl; provided that at least one Z 1  is other than NO 2 ; Z 2  is for example unsubstituted or substituted C 7 -C 20 aroyl; R 1 , R 2 , R 3 , R 4 , R 5  and R 6  for example are hydrogen, halogen, or unsubstituted or substituted C 1 -C 20 alkyl, unsubstituted or substituted C 6 -C 20 aryl, or unsubstituted or substituted C 4 -C 20 heteroaryl; R 9 , R 10 , R 11 , R 12  and R 13  for example are hydrogen, halogen, OR 16 , unsubstituted or substituted C 1 -C 20 alkyl; provided that R 9  and R 13  are neither hydrogen nor fluorine; R 14  is for example unsubstituted or substituted C 6 -C 20 aryl or C 3 -C 20 heteroaryl Q is for example C 6 -C 20 arylene or C 3 -C 20 heteroarylene; Q 1  is —C 1 -C 20 alkylene-CO—; Q 2  is naphthoylene; Q 3  is for example phenylene; L is for example O-alkylene-O—; R 15  is for example hydrogen or C 1 -C 20 alkyl; R 20  is for example hydrogen, or unsubstituted or substituted C 1 -C 20 alkyl; are effective photoinitiators.

The invention pertains to new oxime ester compounds based on specificcarbazole derivatives and their use as photoinitiators inphotopolymerizable compositions, in particular in photoresistformulations, for example in resins for black matrix in color filterapplications.

Oxime ester compounds having carbazole moieties are known in the art asphotoinitiators. For example WO02/100903 discloses correspondingcompounds. The broad generic scopes of JP2006-030809-A, JP2006-162784and JP2009-128419 also encompass compounds with a carbazole moiety. InJP2005-099258-A dimeric carbazole compounds are described.

However, none of the specific examples provide compounds with thefeatures as given for the compounds of the invention.

In photopolymerization technology there still exists a need for highlyreactive, easy to prepare and easy to handle photoinitiators. Forexample, in color filter resist applications, highly pigmented resistsare required for the high color quality property. With the increase ofthe pigment content, the curing of color resists becomes more difficult.Hence, photoinitiators having a high sensitivity are required. Inaddition, also such new photoinitiators must meet the high requirementsof the industry regarding properties like, for example, easy handling,high solubility, thermal stability and storage stability. Furthermorethe initiators in display applications should contribute to surfacesmoothness of a pattern, adhesiveness to the substrate etc. Further,easy access to corresponding intermediates for the preparation of thecompounds should be given. Thus, there is still is a need forphotoinitiator compounds providing a perfect balance of the requirementsas given above. E.g. an acceptable balance between accessability in viewof preparation methods and processes as well as properties of thecompound as for example sensitivity, solubility etc.

It now has been found, that selected compounds in particular providethese properties. Thus, subject of the invention are compounds of theformula I, II, III, IV or V

wherein

Z is

or C₄-C₂₀heteroaroyl which is unsubstituted or substituted by one ormore identical or different R₁₀;Z₁ independently of each other are NO₂, C₇-C₂₀aroyl orC₄-C₂₀heteroaroyl, where C₇-C₂₀aroyl or C₄-C₂₀heteroaroyl isunsubstituted or substituted by one or more identical or different R₁₀;provided that in formula III at least one Z₁ is other than NO₂;Z₂ is C₇-C₂₀aroyl or C₄-C₂₀heteroaroyl, where C₇-C₁₈aroyl orC₄-C₂₀heteroaroyl are unsubstituted or substituted by one or moreidentical or different R₁₀; or Z₂ is NO₂;R₁, R₂, R₃, R₄, R₅ and R₆ independently of each other are hydrogen,halogen, OR₁₆, SR₁₇, NR₁₈R₁₉, or C₁-C₂₀alkyl which is unsubstituted orsubstituted by one or more halogen, OR₁₆, COOR₁₆, CONR₁₈R₁₉ or NR₁₈R₁₉;or R₁, R₂, R₃, R₄, R₅ and R₆ independently of each other are C₆-C₂₀aryl,or C₄-C₂₀heteroaryl, each of which is unsubstituted or substituted byone or more C₁-C₆alkyl, C₁-C₄haloalkyl or halogen;R₉, R₁₀, R₁₁, R₁₂ and R₁₃ independently of each other are hydrogen,halogen, OR₁₆, SR₁₇, NR₁₈R₁₉, CN, NO₂ or C₂-C₂₀alkyl which isinterrupted by one or more O, S or NR₂₁, wherein the interruptedC₂-C₂₀alkyl is unsubstituted or substituted by one or more halogen,OR₁₆, COOR₁₆, SR₁₇, CONR₁₈R₁₉, C₆-C₂₀aryl, C₃-C₂₀heteroaryl orC₃-C₂₀cycloalkyl, C₃-C₂₀cycloalkyl interrupted by one or more O, S,NR₂₁;or R₉, R₁₀, R₁₁, R₁₂ and R₁₃ independently of each other are C₁-C₂₀alkylwhich is unsubstituted or substituted by one or more halogen, OR₁₆,SR₁₇, COOR₁₆, CONR₁₈R₁₉, NR₁₈R₁₉, phenyl, C₃-C₈-cycloalkyl,C₃-C₂₀heteroaryl or M;provided that R₉ and R₁₃ are neither hydrogen nor fluorine;R₁₄ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstituted orsubstituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₆, SR₁₇, NR₁₈R₁₉, PO(OC_(k)H_(2k+1))₂, SO—C₁-C₁₀alkyl,SO₂—C₁-C₁₀alkyl, M,

or by C₂-C₂₀alkyl which is interrupted by one or more O, CO, S, C(O)O,OC(O), phenylene, naphthylene or by NR₂₁, or each of which C₆-C₂₀aryl orC₃-C₂₀heteroaryl is substituted by one or more C₁-C₂₀alkyl which isunsubstituted or substituted by one or more halogen, COOR₁₆, CONR₁₈R₁₉,phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇, NR₁₈R₁₉ or by M;Q is C₆-C₂₀arylene or C₃-C₂₀heteroarylene each of which is unsubstitutedor substituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₆, SR₁₇, NR₁₈R₁₉, PO(OC_(k)H_(2k+1))₂, SO—C₁-C₁₀alkyl,SO₂—C₁-C₁₀alkyl, M,

or by C₂-C₂₀alkyl which is interrupted by one or more O, CO, S, C(O)O,OC(O), phenylene, naphthylene or by NR₂₁, or each of which C₆-C₂₀aryleneor C₃-C₂₀heteroarylene is substituted by one or more C₁-C₂₀alkyl whichis unsubstituted or substituted by one or more halogen, COOR₁₆,CONR₁₈R₁₉, phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl,C₆-C₂₀aryloxycarbonyl, C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇, NR₁₈R₁₉or by M;Q₁ is a direct bond, C₁-C₂₀alkylene, C₁-C₂₀alkenylene, whichC₁-C₂₀alkylene OR C₁-C₂₀alkenylene are unsubstituted or substituted byone or more halogen, OR₁₆, COOR₁₆, NR₁₈R₁₉, C₁-C₂₀heteroaryl CONR₁₈R₁₉,

phenyl or by phenyl substituted by halogen, C₁-C₂₀alkyl, C₁-C₄haloalkyl,OR₁₆, SR₁₇, or NR₁₈R₁₉;or Q₁ is C₃-C₁₀cycloalkylene or C₃-C₁₀cycloalkenylene, both of whichoptionally are interrupted by O, CO or NR₂₁;or Q₁ is C₂-C₂₀alkylene interrupted by one or more O or C₂-C₂₀alkenyleneinterrupted by one or more O, which interrupted C₂-C₂₀alkylene orC₂-C₂₀alkenylene is unsubstituted or substituted by one or more halogen,OR₁₆, COOR₁₆, NR₁₈R₁₉, C₁-C₂₀heteroaryl, CONR₁₈R₁₉,

phenyl or by phenyl substituted by halogen, C₁-C₂₀alkyl, C₁-C₄haloalkyl,OR₁₆, SR₁₇, or NR₁₈R₁₉;or Q₁ is phenylene, naphthylene, coumarinylene or C₁-C₂₀heteroarylene,each of which is unsubstituted or substituted by one or moreC₁-C₁₂alkyl, phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂, OR₁₆, SR₁₇,NR₁₈R₁₉ or by C₃-C₁₀cycloalkyl which optionally is interrupted by O, COor NR₂₁;or Q₁ is phenylene-O* or naphthylene-O*, each of which is unsubstitutedor substituted by one or more C₁-C₆alkyl, halogen, phenyl, OR₁₆, SR₁₇,or NR₁₈R₁₉;or Q₁ is C₁-C₂₀alkylene-CO* or phenylene-CO* which is unsubstituted orsubstituted by by one or more C₁-C₆alkyl, halogen, phenyl, OR₁₆, SR₁₇,or NR₁₈R₁₉;or Q₁ is C₁-C₂₀alkylene-O—CO* which is optionally interrupted by one ormore O and which interrupted or uninterrupted C₁-C₂₀alkylene-O—CO* isunsubstituted or substituted by one or more OH;or Q₁ is phenylene-O—CO* which is unsubstituted or substituted by one ormore C₁-C₆alkyl, C₁-C₄haloalkyl, halogen, phenyl, OR₁₆, SR₁₇, orNR₁₈R₁₉;

or Q₁ is

p is an integer 1 or 2;where the asterix in the definitions for Q₁ denotes the bond to L;

Q₂ is

where the double asterix denotes the bond to the carbazyl group andwherein the naphthyleneoyl or phenyleneoyl is unsubstituted orsubstituted by one or more idenical or different R₁₀;Q₃ is phenylene, naphthylene or C₃-C₁₂heteroarylene, all of which aresubstituted by

M is

G is NO₂ or —COR₂₈;

L is C₁-C₂₀alkylene, C₂-C₁₂alkenylene, O-phenylene-O, O-naphthylene-O,S—C₁-C₂₀alkylene-S, S-phenylene-S, S-naphthylene-S,C₂-C₂₀alkylene which is interrupted by one or more groups selected fromthe group consisting of O, S, CO, (CO)O, O(CO), phenylene andnaphthylene,or L is O—C₁-C₂₀alkylene-O, O—C₂-C₂₀alkylene-O which is interrupted byone or more groups selected from the group consisting of O, S, CO,(CO)O, O(CO), phenylene and naphthylene,or L is S—C₂-C₂₀alkylene-S which is interrupted by one or more groupsselected from the group consisting of O, S, CO, (CO)O, O(CO), phenyleneand naphthylene, wherein all radicals L as defined are unsubstituted orsubstituted by one or more halogen;R″₁₄ is C₁-C₂₀alkyl which is unsubstituted or substituted by phenyl orby phenyl which is substituted by one or more halogen, C₁-C₂₀alkyl,C₁-C₄haloalkyl, OR₁₆, SR₁₇ or by NR₁₈R₁₉;or R″₁₄ is C₂-C₂₀alkyl which is interrupted by one or more O, CO, S,C(O)O, OC(O), phenylene, naphthylene or NR₂₁, wherein the interruptedC₂-C₂₀alkyl is unsubstituted or substituted by one or more halogen,OR₁₆, COOR₁₆, CONR₁₈R₁₉, phenyl or by phenyl which is substituted byOR₁₆, SR₁₇ or NR₁₈R₁₉;or R″₁₄ is CN, CONR₁₈R₁₉, NO₂, C₁-C₄haloalkyl, S(O)_(m)—C₁-C₆alkyl;S(O)_(m)-phenyl which is unsubstituted or substituted by C₁-C₁₂alkyl orSO₂—C₁-C₆alkyl;or R″₁₄ is SO₂O-phenyl which is unsubstituted or substituted byC₁-C₁₂alkyl; or is diphenyl phosphinoyl or di-(C₁-C₄alkoxy)-phosphinoyl;or R″₁₄ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstitutedor substituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₆, SR₁₇, NR₁₈R₁₉, PO(OC_(k)H_(2k+1))₂, SO—C₁-C₁₀alkyl,SO₂—C₁-C₁₀alkyl, or by C₂-C₂₀alkyl which is interrupted by one or moreO, CO, S, C(O)O, OC(O), phenylene, naphthylene or by NR₂₁, or each ofwhich is substituted by one or more C₁-C₂₀alkyl which is unsubstitutedor substituted by one or more halogen, COOR₁₆, CONR₁₈R₁₉, phenyl,C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇ or by NR₁₈R₁₉;R₁₅ is hydrogen, C₃-C₈cycloalkyl, C₂-C₅alkenyl, C₁-C₂₀alkoxy orC₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, phenyl, C₁-C₂₀alkylphenyl or CN; or R₁₅ is phenyl or naphthyleach of which is unsubstituted or substituted by one or more C₁-C₆alkyl,C₁-C₄haloalkyl, halogen, CN, OR₁₆, SR₁₇ or NR₁₈R₁₉; or R₁₅ isC₃-C₂₀heteroaryl, benzyloxy or phenoxy, each of is unsubstituted orsubstituted by one or more C₁-C₆alkyl, C₁-C₄haloalkyl or halogen;k is an integer 1-10;m is an integer 1 or 2;R′₁₄ has one of the meanings as given for R₁₄ or is C₁-C₂₀alkyl;R′₁₅ has one of the meanings as given for R₁₅;X₁ is O, CO, S or a direct bond;

X₂ is O, S, SO or SO₂; X₃ is O, S or NR′₂₀;

R₁₆ is hydrogen, phenyl-C₁-C₃alkyl, C₁-C₂₀alkyl, which is unsubstitutedor substituted by one or more halogen, OH, SH, CN, C₃-C₆alkenoxy,O(C₁-C₄alkyl), OCH₂CH₂CN, OCH₂CH₂(CO)O(C₁-C₄alkyl), O(CO)—(C₁-C₄alkyl),O(CO)—(C₂-C₄)alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C₁-C₄alkyl),C₃-C₂₀cycloalkyl, SO₂—(C₁-C₄haloalkyl), O(C₁-C₄haloalkyl),O(C₁-C₂₀arylene)-M, or by C₃-C₂₀cycloalkyl which is interrupted by oneor more O;or R₁₆ is C₂-C₂₀alkyl which is interrupted by one or more O, S or NR₂₁,which interrupted C₂-C₂₀alkyl is unsubstituted or substituted byO—C₆-C₂₀arylene-M, in which O—C₆-C₂₀arylene-M, the arylene isunsubstituted or substituted by one or more C₁-C₆alkyl or O(C₁-C₆alkyl);or R₁₆ is (CH₂CH₂O)_(n+1)H, (CH₂CH₂O)_(n)(CO)—(C₁-C₈alkyl),C₁-C₈alkanoyl, C₂-C₁₂alkenyl, C₃-C₆alkenoyl, or C₃-C₂₀cycloalkyl whichis uninterrupted or interrupted by one or more O, S, CO or NR₂₁;or R₁₆ is C₁-C₈alkyl-C₃-C₁₀cycloalkyl which is uninterrupted orinterrupted by one or more O;or R₁₆ is benzoyl which is unsubstituted or substituted by one or moreC₁-C₆alkyl, halogen, OH, or C₁-C₃alkoxy;or R₁₆ is phenyl, naphthyl or C₃-C₂₀heteroaryl, each of which isunsubstituted or substituted by one or more halogen, OH, C₁-C₁₂alkyl,C₁-C₁₂alkoxy, CN, NO₂, phenyl-C₁-C₃alkyloxy, phenoxy,C₁-C₁₂alkylsulfanyl, phenylsulfanyl, N(C₁-C₁₂alkyl)₂, diphenylamino or

n is 1-20;R₁₇ is hydrogen, C₂-C₁₂alkenyl, C₃-C₂₀cycloalkyl or phenyl-C₁-C₃alkyl,wherein the C₂-C₁₂alkenyl, C₃-C₂₀cycloalkyl or phenyl-C₁-C₃alkyl isuninterrupted or interrupted by one or more O, S, CO or NR₂₁;or R₁₇ is C₁-C₂₀alkyl which is unsubstituted or substituted by one ormore OH, SH, CN, C₃-C₆alkenoxy, OCH₂CH₂CN, OCH₂CH₂(CO)O(C₁-C₄alkyl),O(CO)—(C₂-C₄)alkenyl, O(CO)—(C₁-C₄alkyl), O(CO)-phenyl, COOR₁₆ orS—C₆-C₂₀arylene-M;or R₁₇ is C₁-C₂₀alkyl which is unsubstituted or substituted by one ormore OH, SH, CN, C₃-C₆alkenoxy, OCH₂CH₂CN, OCH₂CH₂(CO)O(C₁-C₄alkyl),O(CO)—(C₂-C₄)alkenyl, O(CO)—(C₁-C₄alkyl), O(CO)-phenyl or COOR₁₆;or R₁₇ is C₂-C₂₀alkyl which is interrupted by one or more O, S, CO orNR₂₁, which interrupted C₂-C₂₀alkyl is unsubstituted or substituted byS—C₆-C₂₀arylene- M;or R₁₇ is (CH₂CH₂O)_(n)H, (CH₂CH₂O)_(n)(CO)—(C₁-C₈alkyl), C₂-C₈alkanoylor C₃-C₆alkenoyl;or R₁₇ is benzoyl which is unsubstituted or substituted by one or moreC₁-C₆alkyl, halogen, OH, C₁-C₄alkoxy or C₁-C₄alkylsulfanyl;or R₁₇ is phenyl, naphthyl or C₃-C₂₀heteroaryl, each of which isunsubstituted or substituted by one or more halogen, C₁-C₁₂alkyl,C₁-C₄haloalkyl, C₁-C₁₂alkoxy, CN, NO₂, phenyl-C₁-C₃alkyloxy, phenoxy,C₁-C₁₂alkylsulfanyl, phenylsulfanyl, N(C₁-C₁₂alkyl)₂, diphenylamino,(CO)O(C₁-C₈alkyl), (CO)—C₁-C₈alkyl, (CO)N(C₁-C₈alkyl)₂ or

R₁₈ and R₁₉ independently of each other are hydrogen, C₁-C₂₀alkyl,C₂-C₄hydroxyalkyl, C₂-C₁₀alkoxyalkyl, C₂-C₅alkenyl, C₃-C₂₀cycloalkyl,phenyl-C₁-C₃alkyl, C₁-C₈alkanoyl, C₁-C₈alkanoyloxy, C₃-C₁₂alkenoyl,SO₂—(C₁-C₄haloalkyl) or benzoyl;or R₁₈ and R₁₉ are phenyl, naphthyl or C₃-C₂₀heteroaryl, each of whichis unsubstituted or substituted by one or more halogen, C₁-C₄haloalkyl,C₁-C₂₀alkoxy, C₁-C₁₂alkyl, benzoyl or C₁-C₁₂alkoxy;or R₁₈ and R₁₉ together with the N-atom to which they are attached forma 5- or 6-membered saturated or unsaturated ring which is uninterruptedor is interrupted by O, S, or NR₂₁, and which 5- or 6-membered saturatedor unsaturated ring is unsubstituted or substituted by one or moreC₁-C₂₀alkyl, C₁-C₂₀alkoxy, ═O, OR₁₆, SR₁₇, NR₃₁R₃₂, COR₄₁, NO₂, halogen,C₁-C₄-haloalkyl, CN, phenyl,

or by C₃-C₂₀cyclalkyl which is uninterrupted or is interrupted by one ormore O, S, CO or NR₂₁;or R₁₈ and R₁₉ together with the N-atom to which they are attached forma group

R₂₀ is hydrogen, COR₄₁ or C₁-C₂₀alkyl which is unsubstituted orsubstituted by one or more halogen, OR₁₆, SR₁₇, COOR₁₆, CONR₁₈R₁₉,NR₁₈R₁₉, PO(OC_(k)H_(2k+1))₂ or M;or R₂₀ is C₂-C₂₀alkyl which is interrupted by one or more O, CO, C(O)O,OC(O) or NR₂₁, wherein the interrupted C₂-C₂₀alkyl is unsubstituted orsubstituted by one or more halogen, OR₁₆, SR₁₇, COOR₁₆, CONR₁₈R₁₉,NR₁₈R₁₉ or M;or R₂₀ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstitutedor substituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₆, SR₁₇, NR₁₈R₁₉, M, Z,

or by C₁-C₂₀alkyl which is interrupted by one or more O, S or NR₂₁, oreach of which C₆-C₂₀aryl or C₃-C₂₀heteroaryl is substituted by one ormore C₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, COOR₁₆, CONR₁₈R₁₉, phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl,C₆-C₂₀aryloxycarbonyl, C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇ orNR₁₈R₁₉;R′₂₀ is hydrogen, COR₄₁ or C₁-C₂₀alkyl which is unsubstituted orsubstituted by one or more halogen, OR₁₆, SR₁₇, COOR₁₆, CONR₁₈R₁₉,NR₁₈R₁₉ or PO(OC_(k)H_(2k+1))₂;or R′₂₀ is C₂-C₂₀alkyl of which is interrupted by one or more O, CO,C(O)O, OC(O) or NR₂₁, wherein the interrupted C₂-C₂₀alkyl isunsubstituted or substituted by one or more halogen, OR₁₆, SR₁₇, COOR₁₆,CONR₁₈R₁₉ or NR₁₈R₁₉;or R′₂₀ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstitutedor substituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₆, SR₁₇, NR₁₈R₁₉,

or by C₁-C₂₀alkyl which is interrupted by one or more O, S or NR₂₁, oreach of which C₆-C₂₀aryl or C₃-C₂₀heteroaryl is substituted by one ormore C₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, COOR₁₆, CONR₁₈R₁₉, phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl,C₆-C₂₀aryloxycarbonyl, C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇ orNR₁₈R₁₉;R₂₁ is hydrogen, C₁-C₂₀alkyl, C₁-C₄haloalkyl or C₂-C₂₀alkyl which isinterrupted by one or more O, CO, C(O)O or OC(CO),or R₂₁ is COR₄₁, phenyl-C₁-C₄alkyl or C₃-C₈cycloalkyl which isuninterrupted or is interrupted by one or more O or CO,or R₂₁ is phenyl or naphthyl both of which are unsubstituted orsubstituted by one or more C₁-C₂₀alkyl, halogen, C₁-C₄haloalkyl, OR₁₆,SR₁₇, NR₁₈R₁₉ or

R₂₂, R₂₃, R₂₄, R₂₅, R₂₆ or R₂₇ independently of each other are hydrogen,COR₄₁, NO₂ or

or one of R₂₂, R₂₃ or R₂₄ and one of R₂₅, R₂₆ or R₂₇ together with X₃and the phenyl rings to which they are attached form a heteroaromaticring system; R₂₈ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which isunsubstituted or substituted by one or more phenyl, halogen,C₁-C₄haloalkyl, CN, NO₂, OR₁₆, SR₁₇, NR₁₈R₁₉ or by C₂-C₂₀alkyl which isinterrupted by one or more O, S or NR₂₁, or each of which C₆-C₂₀aryl orC₃-C₂₀heteroaryl is substituted by one or more C₁-C₂₀alkyl which isunsubstituted or substituted by one or more halogen, COOR₁₆, CONR₁₈R₁₉,phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇, or NR₁₈R₁₉;

R₂₉ is COOR₁₆, CONR₁₈R₁₉, (CO)R₁₆; or R₂₉ has one of the meanings givenfor R₁₈ and R₁₉;R₃₀ is COOR₁₆, CONR₁₈R₁₉, (CO)R₁₆; or R₃₀ has one of the meanings givenfor R₁₆;R₃₁ and R₃₂ independently of each other are hydrogen, C₁-C₂₀alkyl,C₁-C₄haloalkyl, C₃-C₁₀cycloalkyl or phenyl;or R₃₁ and R₃₂ together with N-atom to which they are attached form a 5-or 6-membered saturated or unsaturated ring, which is uninterrupted oris interrupted by O, S or NR₂₁, and which 5- or 6-membered saturated orunsaturated ring is not condensed or to which 5- or 6-membered saturatedor unsaturated ring a benzene ring is condensed;R₃₃, R₃₄, R₃₅, R₃₆, R₃₇, R₃₈, R₃₉ and R₄₀ independently of each otherare hydrogen,

NO₂, COR₄₁, C₁-C₂₀alkyl, C₁-C₄haloalkyl, OR₁₆, SR₁₇, NR₁₈R₁₉, halogen,CN, phenyl or C₃-C₂₀cycloalkyl which is uninterrupted or is interruptedby one or more O, S, CO or NR₂₁;or R₃₅ and R₃₆ or R₃₇ and R₃₈ or both, R₃₅ and R₃₆ and R₃₇ and R₃₈ are

R₄₁ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstituted orsubstituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₆, SR₁₇, NR₁₈R₁₉ or by C₂-C₂₀alkyl which is interrupted by one ormore O, S or NR₂₁, or each of which C₆-C₂₀aryl or C₃-C₂₀heteroaryl issubstituted by one or more C₁-C₂₀alkyl which is unsubstituted orsubstituted by one or more halogen, COOR₁₆, CONR₁₈R₁₉, phenyl,C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇, or NR₁₈R₁₉;

or R₄₁ is

or R₄₁ is hydrogen, OH, C₁-C₂₀alkyl, C₁-C₄haloalkyl, C₂-C₂₀alkyl whichis interrupted by one or more O, CO or NR₂₁, or R₄₁ is C₃-C₂₀cycloalkylwhich is uninterrupted or is interrupted by O, S, CO or NR₂₁.;R₄₂ is hydrogen, C₃-C₈cycloalkyl, C₂-C₅alkenyl, C₁-C₂₀alkoxy or isC₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, phenyl, C₁-C₂₀alkylphenyl or CN;or R₄₂ is phenyl or naphthyl, both of which are unsubstituted orsubstituted by one or more C₁-C₆alkyl, C₁-C₄haloalkyl, halogen, CN,OR₁₆, SR₁₇ or NR₁₈R₁₉;or R₄₂ is benzyloxy or phenoxy both of which are unsubstituted orsubstituted one or more C₁-C₆alkyl, C₁-C₄haloalkyl or halogen.

Interesting are compounds of the formula I, II, II, IV or V wherein

Z is

or C₄-C₂₀heteroaroyl which is unsubstituted or substituted by one ormore identical or different R₁₀;Z₁ independently of each other are NO₂, C₇-C₂₀aroyl orC₄-C₂₀heteroaroyl, where C₇-C₂₀aroyl or C₄-C₂₀heteroaroyl isunsubstituted or substituted by one or more identical or different R₁₀;provided that at least one Z₁ is other than NO₂;Z₂ is C₇-C₂₀aroyl or C₄-C₂₀heteroaroyl, where C₇-C₁₈aroyl orC₄-C₂₀heteroaroyl are unsubstituted or substituted by one or moreidentical or different R₁₀;R₁, R₂, R₃, R₄, R₅ and R₆ independently of each other are hydrogen,halogen, OR₁₆, SR₁₇, NR₁₈R₁₉, or C₁-C₂₀alkyl which is unsubstituted orsubstituted by one or more halogen, OR₁₆, COOR₁₆, CONR₁₈R₁₉ or NR₁₈R₁₉;or R₁, R₂, R₃, R₄, R₅ and R₆ independently of each other are C₆-C₂₀aryl,or C₄-C₂₀heteroaryl, each of which is unsubstituted or substituted byone or more C₁-C₆alkyl, C₁-C₄haloalkyl or halogen;R₉, R₁₀, R₁₁, R₁₂ and R₁₃ independently of each other are hydrogen,halogen, OR₁₆, SR₁₇, NR₁₈R₁₉, CN, NO₂ or C₂-C₂₀alkyl which isinterrupted by one or more O, S or NR₂₁, wherein the interruptedC₂-C₂₀alkyl is unsubstituted or substituted by one or more halogen,OR₁₆, COOR₁₆, SR₁₇, CONR₁₈R₁₉, C₆-C₂₀aryl, C₃-C₂₀heteroaryl orC₃-C₂₀cycloalkyl, C₃-C₂₀cycloalkyl interrupted by one or more O, S,NR₂₁;or R₉, R₁₀, R₁₁, R₁₂ and R₁₃ independently of each other are C₁-C₂₀alkylwhich is unsubstituted or substituted by one or more halogen, OR₁₆,SR₁₇, COOR₁₆, CONR₁₈R₁₉, NR₁₈R₁₉, phenyl, C₃-C₈-cycloalkyl,C₃-C₂₀heteroaryl or M;provided that R₉ and R₁₃ are neither hydrogen nor fluorine;R₁₄ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstituted orsubstituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₆, SR₁₇, NR₁₈R₁₉, PO(OC_(k)H_(2k+1))₂, SO—C₁-C₁₀alkyl,SO₂—C₁-C₁₀alkyl, M,

or by C₂-C₂₀alkyl which is interrupted by one or more O, CO, S, C(O)O,OC(O), phenylene, naphthylene or by NR₂₁, or each of which C₆-C₂₀aryl orC₃-C₂₀heteroaryl is substituted by one or more C₁-C₂₀alkyl which isunsubstituted or substituted by one or more halogen, COOR₁₆, CONR₁₈R₁₉,phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇, NR₁₈R₁₉ or by M;Q is C₆-C₂₀arylene or C₃-C₂₀heteroarylene each of which is unsubstitutedor substituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₆, SR₁₇, NR₁₈R₁₉, PO(OC_(k)H_(2k+1))₂, SO—C₁-C₁₀alkyl,SO₂—C₁-C₁₀alkyl, M,

or by C₂-C₂₀alkyl which is interrupted by one or more O, CO, S, C(O)O,OC(O), phenylene, naphthylene or by NR₂₁, or each of which C₆-C₂₀aryleneor C₃-C₂₀heteroarylene is substituted by one or more C₁-C₂₀alkyl whichis unsubstituted or substituted by one or more halogen, COOR₁₆,CONR₁₈R₁₉, phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl,C₆-C₂₀aryloxycarbonyl, C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇, NR₁₈R₁₉or by M;Q₁ is—C₁-C₂₀alkylene-CO-*, where the asterix denotes the bond to L;

Q₂ is

where the double asterix denotes the bond to the carbazyl group andwherein the naphthoyl is unsubstituted or substituted by one or moreidenical or different R₁₀;

Q₃ is phenylene, naphthylene or C₃-C₁₂heteroarylene, all of which aresubstituted by

M is

G is NO₂ or —COR₂₈;

L is O—C₁-C₂₀alkylene-O, O—C₂-C₂₀alkylene-O which is interrupted by oneor more nonadjacent O-atoms or is C₂-C₁₂alkenylene;R″₁₄ is C₁-C₂₀alkyl which is unsubstituted or substituted by phenyl orby phenyl which is substituted by one or more halogen, C₁-C₂₀alkyl,C₁-C₄haloalkyl, OR₁₆, SR₁₇ or by NR₁₈R₁₉;or R″₁₄ is C₂-C₂₀alkyl which is interrupted by one or more O, CO, S,C(O)O, OC(O), phenylene, naphthylene or NR₂₁, wherein the interruptedC₂-C₂₀alkyl is unsubstituted or substituted by one or more halogen,OR₁₆, COOR₁₆, CONR₁₈R₁₉, phenyl or by phenyl which is substituted byOR₁₆, SR₁₇ or NR₁₈R₁₉;or R″₁₄ is CN, CONR₁₈R₁₉, NO₂, C₁-C₄haloalkyl, S(O)_(m)—C₁-C₆alkyl;S(O)_(m)-phenyl which is unsubstituted or substituted by C₁-C₁₂alkyl orSO₂—C₁-C₆alkyl;or R″₁₄ is SO₂O-phenyl which is unsubstituted or substituted byC₁-C₁₂alkyl; or is diphenyl phosphinoyl or di-(C₁-C₄alkoxy)-phosphinoyl;or R″₁₄ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstitutedor substituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₆, SR₁₇, NR₁₈R₁₉, PO(OC_(k)H_(2k+1))₂, SO—C₁-C₁₀alkyl,SO₂—C₁-C₁₀alkyl, or by C₂-C₂₀alkyl which is interrupted by one or moreO, CO, S, C(O)O, OC(O), phenylene, naphthylene or by NR₂₁, or each ofwhich is substituted by one or more C₁-C₂₀alkyl which is unsubstitutedor substituted by one or more halogen, COOR₁₆, CONR₁₈R₁₉, phenyl,C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇ or by NR₁₈R₁₉;R₁₅ is hydrogen, C₃-C₈cycloalkyl, C₂-C₅alkenyl, C₁-C₂₀alkoxy orC₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, phenyl, C₁-C₂₀alkylphenyl or CN; or R₁₅ is phenyl or naphthyleach of which is unsubstituted or substituted by one or more C₁-C₆alkyl,C₁-C₄haloalkyl, halogen, CN, OR₁₆, SR₁₇ or NR₁₈R₁₉;or R₁₅ is C₃-C₂₀heteroaryl, benzyloxy or phenoxy, each of isunsubstituted or substituted by one or more C₁-C₆alkyl, C₁-C₄haloalkylor halogen;k is an integer 1-10;m is an integer 1 or 2;R′₁₄ has one of the meanings as given for R₁₄;R′₁₅ has one of the meanings as given for R₁₅,X₁ is O, CO, S or a direct bond;

X₂ is O, S, SO or SO₂; X₃ is O, S or NR′₂₀;

R₁₆ is hydrogen, phenyl-C₁-C₃alkyl, C₁-C₂₀alkyl which is unsubstitutedor substituted by one or more halogen, OH, SH, CN, C₃-C₆alkenoxy,OCH₂CH₂CN, OCH₂CH₂(CO)O(C₁-C₄alkyl), O(CO)—(C₁-C₄alkyl),O(CO)—(C₂-C₄)alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C₁-C₄alkyl),C₃-C₂₀cycloalkyl, SO₂—(C₁-C₄haloalkyl), O(C₁-C₄haloalkyl),O(C₁-C₂₀arylene)-M, or by C₃-C₂₀cycloalkyl which is interrupted by oneor more O;or R₁₆ is C₂-C₂₀alkyl which is interrupted by one or more O, S or NR₂₁;or R₁₆ is (CH₂CH₂O)_(n+1)H, (CH₂CH₂O)_(n)(CO)—(C₁-C₈alkyl),C₁-C₈alkanoyl, C₂-C₁₂alkenyl, C₃-C₆alkenoyl, or C₃-C₂₀cycloalkyl whichis uninterrupted or interrupted by one or more O, S, CO or NR₂₁;or R₁₆ is C₁-C₈alkyl-C₃-C₁₀cycloalkyl which is uninterrupted orinterrupted by one or more O;or R₁₆ is benzoyl which is unsubstituted or substituted by one or moreC₁-C₆alkyl, halogen, OH, or C₁-C₃alkoxy;or R₁₆ is phenyl, naphthyl or C₃-C₂₀heteroaryl, each of which isunsubstituted or substituted by one or more halogen, OH, C₁-C₁₂alkyl,C₁-C₁₂alkoxy, CN, NO₂, phenyl-C₁-C₃alkyloxy, phenoxy,C₁-C₁₂alkylsulfanyl, phenylsulfanyl, N(C₁-C₁₂alkyl)₂, diphenylamino or

n is 1-20;R₁₇ is hydrogen, C₂-C₁₂alkenyl, C₃-C₂₀cycloalkyl or phenyl-C₁-C₃alkyl,wherein the C₂-C₁₂alkenyl, C₃-C₂₀cycloalkyl or phenyl-C₁-C₃alkyl isuninterrupted or interrupted by one or more O, S, CO or NR₂₁;or R₁₇ is C₁-C₂₀alkyl which is unsubstituted or substituted by one ormore OH, SH, CN, C₃-C₆alkenoxy, OCH₂CH₂CN, OCH₂CH₂(CO)O(C₁-C₄alkyl),O(CO)—(C₂-C₄)alkenyl, O(CO)—(C₁-C₄alkyl), O(CO)-phenyl or COOR₁₆;or R₁₇ is C₂-C₂₀alkyl which is interrupted by one or more O, S, CO orNR₂₁;or R₁₇ is (CH₂CH₂O)_(n)H, (CH₂CH₂O)_(n)(CO)—(C₁-C₈alkyl), C₂-C₈alkanoylor C₃-C₆alkenoyl;or R₁₇ is benzoyl which is unsubstituted or substituted by one or moreC₁-C₆alkyl, halogen, OH, C₁-C₄alkoxy or C₁-C₄alkylsulfanyl;or R₁₇ is phenyl, naphthyl or C₃-C₂₀heteroaryl, each of which isunsubstituted or substituted by one or more halogen, C₁-C₁₂alkyl,C₁-C₄haloalkyl, C₁-C₁₂alkoxy, CN, NO₂, phenyl-C₁-C₃alkyloxy, phenoxy,C₁-C₁₂alkylsulfanyl, phenylsulfanyl, N(C₁-C₁₂alkyl)₂, diphenylamino,(CO)O(C₁-C₈alkyl), (CO)—C₁-C₈alkyl, (CO)N(C₁-C₈alkyl)₂ or

R₁₈ and R₁₉ independently of each other are hydrogen, C₁-C₂₀alkyl,C₂-C₄hydroxyalkyl, C₂-C₁₀alkoxyalkyl, C₂-C₅alkenyl, C₃-C₂₀cycloalkyl,phenyl-C₁-C₃alkyl, C₁-C₈alkanoyl, C₁-C₈alkanoyloxy, C₃-C₁₂alkenoyl,SO₂—(C₁-C₄haloalkyl) or benzoyl;or R₁₈ and R₁₉ are phenyl, naphthyl or C₃-C₂₀heteroaryl, each of whichis unsubstituted or substituted by one or more halogen, C₁-C₄haloalkyl,C₁-C₂₀alkoxy, C₁-C₁₂alkyl, benzoyl or C₁-C₁₂alkoxy;or R₁₈ and R₁₉ together with the N-atom to which they are attached forma 5- or 6-membered saturated or unsaturated ring which is uninterruptedor is interrupted by O, S, or NR₂₁, and which 5- or 6-membered saturatedor unsaturated ring is unsubstituted or substituted by one or moreC₁-C₂₀alkyl, C₁-C₂₀alkoxy, ═O, OR₁₆, SR₁₇, NR₃₁R₃₂, COR₄₁, NO₂, halogen,C₁-C₄-haloalkyl, CN, phenyl,

or by C₃-C₂₀cyclalkyl which is uninterrupted or is interrupted by one ormore O, S, CO or NR₂₁;

or R₁₈ and R₁₉ together with the N-atom to which they are attached forma group

R₂₀ is hydrogen, COR₄₁ or C₁-C₂₀alkyl which is unsubstituted orsubstituted by one or more halogen, OR₁₆, SR₁₇, COOR₁₆, CONR₁₈R₁₉,NR₁₈R₁₉, PO(OC_(k)H_(2k+1))₂ or M;or R₂₀ is C₂-C₂₀alkyl of which is interrupted by one or more O, CO,C(O)O, OC(O) or NR₂₁, wherein the interrupted C₂-C₂₀alkyl isunsubstituted or substituted by one or more halogen, OR₁₆, SR₁₇, COOR₁₆,CONR₁₈R₁₉, NR₁₈R₁₉ or M;or R₂₀ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstitutedor substituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₆, SR₁₇, NR₁₈R₁₉, M, Z,

or by C₁-C₂₀alkyl which is interrupted by one or more O, S or NR₂₁, oreach of which C₆-C₂₀aryl or C₃-C₂₀heteroaryl is substituted by one ormore C₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, COOR₁₆, CONR₁₈R₁₉, phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl,C₆-C₂₀aryloxycarbonyl, C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SIR₁₇ orNR₁₈R₁₉;R′₂₀ is hydrogen, COR₄₁ or C₁-C₂₀alkyl which is unsubstituted orsubstituted by one or more halogen, OR₁₆, SR₁₇, COOR₁₆, CONR₁₈R₁₉,NR₁₈R₁₉ or PO(OC_(k)H_(2k+1))₂;or R′₂₀ is C₂-C₂₀alkyl of which is interrupted by one or more O, CO,C(O)O, OC(O) or NR₂₁, wherein the interrupted C₂-C₂₀alkyl isunsubstituted or substituted by one or more halogen, OR₁₆, SR₁₇, COOR₁₆,CONR₁₈R₁₉ or NR₁₈R₁₉;or R′₂₀ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstitutedor substituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₆, SR₁₇, NR₁₈R₁₉,

or by C₁-C₂₀alkyl which is interrupted by one or more O, S or NR₂₁, oreach of which C₆-C₂₀aryl or C₃-C₂₀heteroaryl is substituted by one ormore C₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, COOR₁₆, CONR₁₈R₁₉, phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl,C₆-C₂₀aryloxycarbonyl, C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇ orNR₁₈R₁₉;R₂₁ is hydrogen, C₁-C₂₀alkyl, C₁-C₄haloalkyl or C₂-C₂₀alkyl which isinterrupted by one or more O, CO, C(O)O or OC(CO),or R₂₁ is COR₄₁, phenyl-C₁-C₄alkyl or C₃-C₈cycloalkyl which isuninterrupted or is interrupted by one or more O or CO,or R₂₁ is phenyl or naphthyl both of which are unsubstituted orsubstituted by one or more C₁-C₂₀alkyl, halogen, C₁-C₄haloalkyl, OR₁₆,SR₁₇, NR₁₈R₁₉ or

R₂₂, R₂₃, R₂₄, R₂₅, R₂₆ or R₂₇ independently of each other are hydrogen,COR₄₁, NO₂ or

or one of R₂₂, R₂₃ or R₂₄ and one of R₂₅, R₂₆ or R₂₇ together with X₃and the phenyl rings to which they are attached form a heteroaromaticring system;R₂₈ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstituted orsubstituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₆, SR₁₇, NR₁₈R₁₉ or by C₂-C₂₀alkyl which is interrupted by one ormore O, S or NR₂₁, or each of which C₆-C₂₀aryl or C₃-C₂₀heteroaryl issubstituted by one or more C₁-C₂₀alkyl which is unsubstituted orsubstituted by one or more halogen, COOR₁₆, CONR₁₈R₁₉, phenyl,C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇, or NR₁₈R₁₉;R₂₉ is COOR₁₆, CONR₁₈R₁₉, (CO)R₁₆; or R₂₉ has one of the meanings givenfor R₁₈ and R₁₉;R₃₀ is COOR₁₆, CONR₁₈R₁₉, (CO)R₁₆; or R₃₀ has one of the meanings givenfor R₁₆;R₃₁ and R₃₂ independently of each other are hydrogen, C₁-C₂₀alkyl,C₁-C₄haloalkyl, C₃-C₁₀cycloalkyl or phenyl;or R₃₁ and R₃₂ together with N-atom to which they are attached form a 5-or 6-membered saturated or unsaturated ring, which is uninterrupted oris interrupted by O, S or NR₂₁, and which 5- or 6-membered saturated orunsaturated ring is not condensed or to which 5- or 6-membered saturatedor unsaturated ring a benzene ring is condensed;R₃₃, R₃₄, R₃₅, R₃₆, R₃₇, R₃₈, R₃₉ and R₄₀ independently of each otherare hydrogen,

NO₂, COR₄₁, C₁-C₂₀alkyl, C₁-C₄haloalkyl, OR₁₆, SR₁₇, NR₁₈R₁₉, halogen,CN, phenyl or C₃-C₂₀cycloalkyl which is uninterrupted or is interruptedby one or more O, S, CO or NR₂₁;or R₃₅ and R₃₆ or R₃₇ and R₃₈ or both, R₃₅ and R₃₆ and R₃₇ and R₃₈ are

R₄₁ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstituted orsubstituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₆, SR₁₇, NR₁₈R₁₉ or by C₂-C₂₀alkyl which is interrupted by one ormore O, S or NR₂₁, or each of which C₆-C₂₀aryl or C₃-C₂₀heteroaryl issubstituted by one or more C₁-C₂₀alkyl which is unsubstituted orsubstituted by one or more halogen, COOR₁₆, CONR₁₈R₁₉, phenyl,C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇ or NR₁₈R₁₉;

or R₄₁ is

or R₄₁ is hydrogen, OH, C₁-C₂₀alkyl, C₁-C₄haloalkyl, C₂-C₂₀alkyl whichis interrupted by one or more O, CO or NR₂₁, or R₄₁ is C₃-C₂₀cycloalkylwhich is uninterrupted or is interrupted by O, S, CO or NR₂₁.

The compounds of the formula I are characterized in that they comprisesubstitutents in both ortho-positions of the benzoyl group and in thatthe substituent R₁₄ at the oxime group is either an aryl or a heteroarylmoiety.

C₁-C₂₀alkyl is linear or branched and is, for example, C₁-C₁₈-, C₁-C₁₄-,C₁-C₁₂-, C₁-C₈-, C₁-C₆-, C₁-C₄alkyl or C₄-C₁₂- or C₄-C₈alkyl. Examplesare methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl,tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl,octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl,octadecyl and icosyl. C₁-C₆alkyl and C₁-C₁₂alkyl have the same meaningsas given above for C₁-C₂₀alkyl up to the corresponding number ofC-atoms.

C₁-C₄haloalkyl is C₁-C₄alkyl as defined above substituted by halogen asdefined below. The alkyl radical is for example halogenated once, twiceor three times, or mono- or poly-halogenated, up to the exchange of allH-atoms by halogen. It is for example C_(n)H_(x)Hal_(y), whereinx+y=2n+1 and Hal is halogen, preferably F. Specific examples arechloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl,especially trifluoromethyl or trichloromethyl.

C₂-C₄hydroxyalkyl means C₂-C₄alkyl, which substituted by one or more, inparticular one or two OH groups. The alkyl radical is linear orbranched. Examples are 2-hydroxyethyl, 1-hydroxyethyl, 1-hydroxypropyl,2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxybutyl, 4-hydroxybutyl,2-hydroxybutyl, 3-hydroxybutyl, 2,3-dihydroxypropyl, or2,4-dihydroxybutyl.

C₂-C₁₀alkoxyalkyl is linear or branched C₂-C₁₀alkyl, which isinterrupted by one 0-atom. C₂-C₁₀alkyl has the same meanings as givenabove for C₁-C₂₀alkyl up to the corresponding number of C-atoms.Examples are methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl,ethoxyethyl, ethoxypropyl, propoxymethyl, propoxyethyl, propoxypropyl.

C₂-C₂₀alkyl which is interrupted by one or more O, CO, S, C(O)O, OC(O),phenylene, naphthylene or NR₂₁, is for example interrupted 1-9, 1-5, 1-3or once or twice by O, CO, S, C(O)O, OC(O), phenylene, naphthylene orNR₂₁. If more than one of the defined interrupting radicals are presentthey are of the same kind or different. Two O-atoms are separated by atleast one methylene group, preferably at least two methylene groups,namely ethylene. The alkyl groups are linear or branched. For examplethe following structural units will occur, —CH₂—CH₂—O—CH₂CH₃,—[CH₂CH₂O]_(y)—CH₃, wherein y=1-9, —(CH₂—CH₂O)₇—CH₂CH₃,—CH₂—CH(CH₃)—O—CH₂—CH₂CH₃, —CH₂—CH(CH₃)—O—CH₂—CH₃, —CH₂—CH₂—S—CH₂CH₃,—CH₂—CH(CH₃)—NR₂₁—CH₂—CH₃, —CH₂—CH₂—COO—CH₂CH₃ or—CH₂—CH(CH₃)—OCO—CH₂—CH₂CH₃, —CH₂—CH₂—O(CO)—CH₂CH₃,—CH₂—CH₂—(CO)O—CH₂CH₃, —CH₂—CH(CH₃)—O(CO)—CH₂—CH₂CH₃,

etc.

C₁-C₂₀alkylene is linear or branched alkylene, for example methylene,ethylene, propylene, 1-methylethylene 1,1-dimethylethylene, butylene,1-methylpropylene, 2-methylpropylene, pentylene, hexylene, heptylene,octylene, nonylene, decylene, dodecylene, tetradecylene, hexadecylene oroctadecylene. In particular, C₁-C₁₂alkylene, for example ethylene,decylene,

C₂-C₂₀alkylene which is interrupted one or more times by O is, forexample, interrupted 1-9 times, for example 1-7 times or once or twiceby O. This produces structural units such as, for example, —CH₂—O—CH₂—,—CH₂—CH₂—O—CH₂—CH₂—,—[CH₂CH₂O]_(y)—, —[CH₂CH₂O]_(y)—CH₂—, where y=1-9,—(CH₂CH₂O)₇CH₂CH₂—, —CH₂—CH(CH₃)—O—CH₂—CH(CH₃)— or—CH₂—CH(CH₃)—O—CH₂—CH₂CH₂—. The interrupting atoms are nonsuccessive.

C₂-C₁₂alkenylene is mono- or polyunsaturated and is, for example,ethenylene, 1-propenylene, 1-butenylene, 3-butenylene, 2-butenylene,1,3-pentadienylene, 5-hexenylene or 7-octenylene.

C₃-C₁₀cycloalkyl and C₃-C₈Cycloalkyl in the context of the presentapplication is to be understood as alkyl which at least comprises onering. It is for example cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cyclooctyl, especially cyclopentyl and cyclohexyl.C₃-C₁₀cycloalkyl in the context of the present invention is also meantto cover bicyclic rings, in other words a bridged ring, such as forexample

and corresponding rings. Further examples are structures like

as well as bridged or fused ring systems, e.g.

etc. are also meant to be covered by the term.

C₃-C₂₀cycloalkyl which is interrupted by O, S, CO or NR₂₁ has themeanings given above for C₃-C₂₀cycloalkyl, wherein at least oneCH₂-group of the alkyl is exchanged by either O, S, CO or NR₂₁. Examplesare structures like

etc.

C₁-C₈alkyl-C₃-C₁₀cycloalkyl is C₃-C₁₀cycloalkyl as defined above whichis substituted by one or more alkyl groups with up to 8 carbon atoms.Examples are

etc. Further, corresponding interrupted C₁-C₈alkyl-C₃-C₁₀cycloalkylinterrupted by one or more O refers to the C₁-C₈alkyl-C₃-C₁₀cycloalkylas defined above, where the interrupting atoms are considered asinterrupting either the C₁-C₈alkyl or the C₃-C₁₀cycloalkyl, or both.

Examples are

etc.

C₁-C₂₀alkoxy is linear or branched and is C₁-C₂₀alkyl, which issubstituted by one-O-atom, namely C₁-C₂₀alkyl-O—. C₁-C₂₀alkyl has thesame meanings as given above for C₁-C₂₀alkyl up to the correspondingnumber of C-atoms. C₁-C₂₀alkoxy is for example C₁-C₁₈-, C₁-C₁₂-,C₁-C₁₀-, C₁-C₈-, C₁-C₄- or C₁-C₃alkoxy. Examples are methoxy, ethoxy,propoxy, isopropoxy, n-butyloxy, sec-butyloxy, isobutyloxy,tert-butyloxy. C₁-C₈alkoxy and C₁-C₄-alkoxy have the same meanings asdescribed above up to the corresponding numbers of C-atoms.

C₁-C₁₂alkylsulfanyl is linear or branched and is C₁-C₁₂alkyl, which issubstituted by one S-atom, namely C₁-C₁₂alkyl-S—. C₁-C₁₂alkyl has thesame meanings as given above for C₁-C₂₀alkyl up to the correspondingnumber of C-atoms. C₁-C₄alkylsulfanyl is linear or branched, forexample, methylsulfanyl, ethylsulfanyl, propylsulfanyl,isopropylsulfanyl, n-butylsulfanyl, sec-butylsulfanyl, isobutylsulfanyl,tert-butylsulfanyl.

Phenyl-C₁-C₃alkyl or phenyl-C₁-C₄alkyl is for example benzyl,phenylethyl, α-methylbenzyl, α,α-dimethylbenzyl, especially benzyl.

Phenyl-C₁-C₃alkyl interrupted by one or more O, S, CO or NR₂₁ isphenyl-C₁-C₃alkyl as defined above, wherein the alkyl moiety isinterrupted by one or two O, S, CO or NR₂₁. If more than one of thedefined interrupting radicals are present they are of the same kind ordifferent. Two O-atoms are separated by a methylene group. The alkylgroups are linear or branched.

Phenyl-C₁-C₃alkoxyl or phenyl-C₁-C₄alkyloxy is for example benzyloxy,phenylethyloxy, α-methylbenzyloxy or α,α-dimethylbenzyloxy, especiallybenzyloxy.

C₂-C₁₂alkenyl or C₂-C₅alkenyl radicals are linear or branched and aremono- or polyunsaturated and are for example C₂-C₁₀-, C₂-C₈-,C₂-C₅-alkenyl e.g. vinyl, allyl, methallyl, 1,1-dimethylallyl,1-butenyl, 3-butenyl, 2-butenyl, 1,3-pentadienyl, 5-hexenyl, 7-octenylor dodecenyl, especially allyl. C₂-C₅alkenyl radicals have the samemeanings as given above for C₂-C₁₂alkenyl radicals up to thecorresponding number of C-atoms.

C₂-C₁₂alkenyl which is interrupted by one or more O, S, CO or NR₂ is forexample interrupted 1-9, 1-5, 1-3 or once or twice by O, S, CO or NR₂₁.If more than one of the interrupting radicals are present they are ofthe same kind or different. Two O-atoms are separated by at least onemethylene group, preferably at least two methylene groups, namelyethylene. The alkenyl groups are linear or branched and are defined asabove. For example following structural units can be formed—CH═CH—O—CH₂CH₃, —CH═CH—O—CH═CH₂ etc.

C₃-C₆alkenoxy is mono or polyunsaturated, linear or branched, and hasone of the meanings given for alkenyl above with the attached oxy groupup to the corresponding number of C-atoms. Examples are allyloxy,methallyloxy, butenyloxy, pentenoxy, 1,3-pentadienyloxy, 5-hexenyloxy.

C₁-C₈alkanoyl=C₁-C₈alkylcarbonyl is linear or branched and is, forexample, C₁-C₆- or C₁-C₄alkanoyl or C₄-C₈alkanoyl. Examples are formyl,acetyl, propionyl, butanoyl, isobutanoyl, pentanoyl, hexanoyl, heptanoylor octanoyl, preferably acetyl.

C₁-C₈alkanoyloxy is C₁-C₈alkanoyl-O—, wherein the C₁-C₈alkanoyl isdefined as above. C₃-C₆alkenoyl is mono or polyunsaturated, linear orbranched, and is for example propenoyl, 2-methyl-propenoyl, butenoyl,pentenoyl, 1,3-pentadienoyl, 5-hexenoyl.

C₆-C₂₀aryloxycarbonyl is for example phenyloxycabonyl [=phenyl-O—(CO)—],naphtyloxycarbonyl, anthryloxycarbonyl etc.

C₅-C₂₀heteroaryloxycarbonyl is C₅-C₂₀heteroaryl-O—CO—.

C₁-C₂₀alkylphenyl refers to phenyl which is substituted by one or morealkyl groups, where the sum of the C atoms is up to 20.

C₆-C₂₀aryl is for example phenyl, naphthyl, anthryl, phenanthryl,pyrene, chrysene, naphthacene, triphenylene etc., in particular phenylor naphthyl, preferably phenyl.

C₇-C₂₀aroyl is meant to be C₆-C₁₉aroyl-CO—, wherein the aroyl is asdefined above up to the corresponding number of C-atoms.

C₆-C₂₀arylene is for example phenylene, biphenylene, o-, m- andp-terphenylene, triphenylphenylene, naphthylene, binaphthylene,anthracenylene, phenanthrylene or pyrenylene, in particular phenylene ornaphthylene, especially phenylene.

Naphthyl is 1-naphthyl or 2-naphthyl.

In the context of the present invention C₃-C₂₀heteroaryl is meant tocomprise either one ring or a multiple ring system, e.g. a fusedring-system. Examples are thienyl, benzo[b]thienyl,naphtho[2,3-b]thienyl, thianthrenyl, furyl, dibenzofuryl, chromenyl,xanthenyl, thioxanthyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl,pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl,indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl,naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl,carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, perimidinyl,phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl,furazanyl, phenoxazinyl, 7-phenanthryl, anthraquinone-2-yl(=9,10-dioxo-9,10-dihydroanthracen-2-yl), 3-benzo[b]thienyl,5-benzo[b]thienyl, 2-benzo[b]thienyl, 4-dibenzofuryl, 4,7-dibenzofuryl,4-methyl-7-dibenzofuryl, 2-xanthenyl, 8-methyl-2-xanthenyl, 3-xanthenyl,2-phenoxyathiinyl, 2,7-phenoxathiinyl, 2-pyrrolyl, 3-pyrrolyl,5-methyl-3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl,2-methyl-4-imidazolyl, 2-ethyl-4-imidazolyl, 2-ethyl-5-imidazolyl,1H-tetrazol-5-yl, 3-pyrazolyl, 1-methyl-3-pyrazolyl,1-propyl-4-pyrazolyl, 2-pyrazinyl, 5,6-dimethyl-2-pyrazinyl,2-indolizinyl, 2-methyl-3-isoindolyl, 2-methyl-1-isoindolyl,1-methyl-2-indolyl, 1-methyl-3-indolyl, 1,5-dimethyl-2-indolyl,1-methyl-3-indazolyl, 2,7-dimethyl-8-purinyl,2-methoxy-7-methyl-8-purinyl, 2-quinolizinyl, 3-isoquinolyl,6-isoquinolyl, 7-isoquinolyl, 3-methoxy-6-isoquinolyl, 2-quinolyl,6-quinolyl, 7-quinolyl, 2-methoxy-3-quinolyl, 2-methoxy-6-quinolyl,6-phthalazinyl, 7-phthalazinyl, 1-methoxy-6-phthalazinyl,1,4-dimethoxy-6-phthalazinyl, 1,8-naphthyridin-2-yl, 2-quinoxalinyl,6-quinoxalinyl, 2,3-dimethyl-6-quinoxalinyl,2,3-dimethoxy-6-quinoxalinyl, 2-quinazolinyl, 7-quinazolinyl,2-dimethylamino-6-quinazolinyl, 3-cinnolinyl, 6-cinnolinyl,7-cinnolinyl, 3-methoxy-7-cinnolinyl, 2-pteridinyl, 6-pteridinyl,7-pteridinyl, 6,7-dimethoxy-2-pteridinyl, 2-carbazolyl, 3-carbazolyl,9-methyl-2-carbazolyl, 9-methyl-3-carbazolyl, β-carbolin-3-yl,1-methyl-β-carbolin-3-yl, 1-methyl-β-carbolin-6-yl, 3-phenanthridinyl,2-acridinyl, 3-acridinyl, 2-perimidinyl, 1-methyl-5-perimidinyl,5-phenanthrolinyl, 6-phenanthrolinyl, 1-phenazinyl, 2-phenazinyl,3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-phenothiazinyl,3-phenothiazinyl, 10-methyl-3-phenothiazinyl, 3-isoxazolyl,4-isoxazolyl, 5-isoxazolyl, 4-methyl-3-furazanyl, 2-phenoxazinyl,10-methyl-2-phenoxazinyl, etc.

C₃-C₂₀heteroaryl in particular is thienyl, benzo[b]thienyl, carbazolyl,thianthrenyl, thioxanthyl, 1-methyl-2-indolyl or 1-methyl-3-indolyl;especially thienyl.

C₄-C₂₀heteroaroyl is meant to be C₃-C₁₉heteroaryl-CO—, wherein theheteroaryl is as defined above, up to the corresponding number ofC-atoms.

C₃-C₂₀heteroarylene is for example furanylene, thiophenylene,pyridinylene, quinolinylene, isoquinolinylene or

in particular thiophenylene.

Substituted aryl radicals phenyl, naphthyl, C₆-C₂₀aryl,C₅-C₂₀heteroaryl, C₆-C₂₀arylene or C₃-C₂₀heteroarylene etc. aresubstituted 1 to 7, 1 to 6 or 1 to 4 times respectively, in particularone, two or three times. It is evident that a defined aryl or heteroarylradical cannot have more substituents than free “CH” or “NH” positionsare at the defined ring. Substituents on the phenyl ring are preferablyin positions 4 or in 3,4-, 3,4,5-, 2,6-, 2,4- or 2,4,6-configuration onthe phenyl ring.

Interrupted radicals which are interrupted once or more times are forexample interrupted 1-19, 1-15, 1-12, 1-9, 1-7, 1-5, 1-4, 1-3 or once ortwice (it is evident, that the number of interrupting atoms depends onthe number of C-atoms to be interrupted). Substituted radicals, whichare substituted once or more times have for example 1-7, 1-5, 1-4, 1-3or one or two identical or different substituents.

A radical substituted by one or more defined substituents is meant tohave either one substituent or more substituents of identical ordifferent definitions as given.

Halogen is fluorine, chlorine, bromine and iodine, especially fluorine,chlorine and bromine, preferably fluorine and chlorine.

If M is a group (X)

for example structures like the following are formed

(R₂₀=C₁-C₂₀alkyl substituted by M),

(R₂₀=C₆-C₂₀aryl substituted by M), etc. If M is a group

(Y)

for example structures like

(R₂₀=C₁-C₂₀alkyl substituted by M) or

(R₂₀=C₆-C₂₀aryl substituted by M), etc. are formed. If M is a group (Z)

for example structures like

(R₂₀=C₁-C₂₀alkyl substituted by M) or

(R₂₀=C₆-C₂₀aryl substituted by M) are formed.

R₁₈ and R₁₉ together with the N-atom to which they are attached form a5- or 6-membered saturated or unsaturated ring which is uninterrupted oris interrupted by O, S, or NR₂₁, saturated or unsaturated rings areformed, for example aziridine, pyrrole, thiazole, pyrrolidine, oxazole,pyridine, 1,3-diazine, 1,2-diazine, piperidine or morpholine.Preferably, if R₁₈ and R₁₉ together with the N-atom to which they areattached form a 5- or 6-membered saturated or unsaturated ring whichoptionally is interrupted by O, S or NR₂₁, 5- or 6-membered saturatedrings which are not interrupted or which are interrupted by O or NR₂₁,in particular by O, are formed.

If R₃₁ and R₃₂ together with N-atom to which they are attached form a 5-or 6-membered saturated or unsaturated ring, which is uninterrupted oris interrupted by O, S or NR₂₁, and which 5- or 6-membered saturated orunsaturated ring is not condensed or to which 5- or 6-membered saturatedor unsaturated ring a benzene ring is condensed saturated or unsaturatedrings are formed, for example aziridine, pyrrole, thiazole, pyrrolidine,oxazole, pyridine, 1,3-diazine, 1,2-diazine, piperidine or morpholine,or corresponding annelated rings, e.g.

etc.

If one of R₂₂, R₂₃ or R₂₄ and one of R₂₅, R₂₆ or R₂₇ together with X₃and the phenyl rings to which they are attached form a heteroaromaticring system which is unsubstituted or substituted, for examplestructures like the following are formed

etc., in particular

If one of R₂₂, R₂₃ or R₂₄ and one of R₂₅, R₂₆ or R₂₇ together with X₃and the phenyl rings to which they are attached form a heteroaromaticring system which is unsubstituted or substituted, preferably acarbazolyl structure is formed.

The terms “and/or” or “or/and” in the present context are meant toexpress that not only one of the defined alternatives (substituents) maybe present, but also several of the defined alternatives (substituents)together, namely mixtures of different alternatives (substituents).

The term “at least” is meant to define one or more than one, for exampleone or two or three, preferably one or two.

The term “optionally substituted” means, that the radical to which itrefers is either unsubstituted or substituted.

Throughout this specification and the claims which follow, unless thecontext requires otherwise, the word “comprise”, or variations such as“comprises” or “comprising”, will be understood to imply the inclusionof a stated integer or step or group of integers or steps but not theexclusion of any other integer or step or group of integers or steps.

The term “(meth)acrylate” in the context of the present application ismeant to refer to the acrylate as well as to the correspondingmethacrylate.

The preferences indicated above for the compounds according to thepresent invention in the context of this invention are intended to referto all categories of the claims, that is to the composition, use,process and preparation process claims as well.

It is to be understood that this invention is not limited to particularcompounds, configurations, method steps, substrates, and materialsdisclosed herein as such compounds, configurations, method steps,substrates, and materials may vary somewhat. It is also to be understoodthat the terminology employed herein is used for the purpose ofdescribing particular embodiments only and is not intended to belimiting since the scope of the present invention is limited only by theappended claims and equivalents thereof.

It must be noted that, as used in this specification and the appendedclaims, the singular forms “a”, “an” and “the” include plural referentsunless the context clearly dictates otherwise.

If nothing else is defined, any terms and scientific terminology usedherein are intended to have the meanings commonly understood by those ofskill in the art to which this invention pertains.

The oxime esters of the formula I are for example prepared by methodsdescribed in the literature, for example by reaction of thecorresponding oximes with an acyl halide, in particular a chloride, oran anhydride in an inert solvent such as for example t-butyl methylether, tetrahydrofurane (THF) or dimethylformamide in the presence of abase, for example triethylamine or pyridine, or in a basic solvent suchas pyridine.

Z, R₁, R₂, R₃, R₄, R₅, R₆, R₂₀, R₁₄, and R₁₅ are as defined above, Halmeans a halogen atom, in particular Cl.

R₁₅ preferably is methyl.

The compounds of the formulae II, III, IV and V are preparedcorrespondingly from the appropriate free oxime compounds IIA, IIIAm IVAand Va

Such reactions are well known to those skilled in the art, and aregenerally carried out at temperatures of −15 to +50° C., preferably 0 to25° C.

Subject of the invention therefore also is a process for the preparationof a compound of the formula I, II, III, IV or V as defined above byreacting the corresponding oxime compound of formula IA, as definedabove, with an acyl halide of the formula (2) or an anhydride of theformula (3)

-   -   wherein Hal is a halogen, in particular Cl, and R₁₅ is as        defined above, in the presence of a base or a mixture of bases.

The oximes required as starting materials can be obtained by a varietyof methods described in standard chemistry textbooks (for instance in J.March, Advanced Organic Chemistry, 4th Edition, Wiley Interscience,1992), or in specialized monographs, for example, S. R. Sandler & W.Karo, Organic functional group preparations, Vol. 3, Academic Press.

One of the most convenient methods is, for example, the reaction ofaldehydes or ketones with hydroxylamine or its salt in polar solventslike dimethylacetamide (DMA), aqueous DMA, ethanol or aqueous ethanol.In that case, a base such as sodium acetate or pyridine is added tocontrol the pH of the reaction mixture. It is well known that the rateof the reaction is pH-dependent, and the base can be added at thebeginning or continuously during the reaction. Basic solvents such aspyridine can also be used as base and/or solvent or cosolvent. Thereaction temperature is generally from room temperature to the refluxingtemperature of the mixture, usually about 20-120° C.

The corresponding ketone intermediates are for example prepared by themethods described in the literature, for example in standard chemistrytextbooks (for instance in J. March, Advanced Organic Chemistry, 4thEdition, Wiley Interscience, 1992). In addition, successiveFriedel-Crafts reaction is effective for synthesis of the intermediates.Such reactions are well known to those skilled in the art.

Another embodiment of the invention is the free oxime compounds of theIA, IIA, IIIA, IVA or VA

wherein Z, Z₁, Z₂, Q, Q₁, Q₂, Q₃, L, R₁, R₂, R₃, R₄, R₅, R₆, R₂₀, andR₁₄ are as defined above.

The preferences for the radicals defined for the compounds of theformula (IA) correspond to the ones as given for the compounds of theformula (I) as given in the remaining context of the description, exceptthat defined oxime ester groups are exchanged by the corresponding freeoxime radical.

Every oxime ester group can exist in two configurations, (Z) or (E). Itis possible to separate the isomers by conventional methods, but it isalso possible to use the isomeric mixture as such as photoinitiatingspecies. Therefore, the invention also relates to mixtures ofconfigurational isomers of compounds of the formula I.

X₁ is for example O, S or a direct bond; or is for example O, CO or adirect bond; or is for example O or a direct bond; or is for example Sor a direct bond; or is for example S or CO; or is for example S and adirect bond; prefereably X₁ is a direct bond.

X₂ is for example O, S or SO; or is for example O or S, preferably O.

X₃ is for example O or NR′₂₀; or is for example S or NR′₂₀; X₃preferably is NR′₂₀.

R₉, R₁₀, R₁₁, R₁₂ and R₁₃ for example independently of each other arehydrogen, halogen, OR₁₆, SR₁₇, NR₁₈R₁₉ or C₂-C₂₀alkyl which isinterrupted by one or more O, S or NR₂₁, wherein the interruptedC₂-C₂₀alkyl is unsubstituted or substituted by one or more halogen,OR₁₆, COOR₁₆, SR₁₇, CONR₁₈R₁₉; or R₉, R₁₀, R₁₁, R₁₂ and R₁₃independently of each other are C₁-C₂₀alkyl which is unsubstituted orsubstituted by one or more halogen, OR₁₆, SR₁₇, COOR₁₆, CONR₁₈R₁₉,NR₁₈R₁₉, phenyl, C₃-C₈-cycloalkyl, C₃-C₂₀heteroaryl or M; provided thatR₉ and R₁₃ are neither hydrogen nor fluorine.

Or R₉, R₁₀, R₁₁, R₁₂ and R₁₃ for example independently of each other arehydrogen, OR₁₆, SR₁₇, NR₁₈R₁₉ or C₂-C₂₀alkyl which is interrupted by oneor more O or NR₂₁, wherein the interrupted C₂-C₂₀alkyl is unsubstitutedor substituted by one or more halogen, OR₁₆, COOR₁₆ or CONR₁₈R₁₉; or R₉,R₁₀, R₁₁, R₁₂ and R₁₃ independently of each other are C₁-C₂₀alkyl whichis unsubstituted or substituted by one or more halogen, OR₁₆, SR₁₇,COOR₁₆, CONR₁₈R₁₉, NR₁₈R₁₉, phenyl, C₃-C₈-cycloalkyl or M; provided thatR₉ and R₁₃ are neither hydrogen nor fluorine.

Or R₉, R₁₀, R₁₁, R₁₂ and R₁₃ for example independently of each other arehydrogen, phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂, OR₁₆, SR₁₇, NR₁₈R₁₉,C₁-C₂₀alkyl or C₁-C₂₀alkyl which is interrupted by one or more O, S, orNR₂₁, provided that R₉ and R₁₃ are neither hydrogen nor fluorine.

Or R₉, R₁₀, R₁₁, R₁₂ and R₁₃ for example independently of each other arehydrogen, OR₁₆, SR₁₇, NR₁₈R₁₉ or C₁-C₂₀alkyl, provided that R₉ and R₁₃are no hydrogen.

Or R₉, R₁₀, R₁₁, R₁₂ and R₁₃ for example independently of each other arehydrogen, OR₁₆, NR₁₈R₁₉ or C₁-C₂₀alkyl, provided that R₉ and R₁₃ areneither hydrogen nor fluorine.

R₁₀ and R₁₂ for example in particular are hydrogen and R₉, R₁₁ and R₁₃independently of each other are, hydrogen, halogen, OR₁₆, SR₁₇, NR₁₈R₁₉or C₂-C₂₀alkyl which is interrupted by one or more O, S or NR₂₁, whereinthe interrupted C₂-C₂₀alkyl is unsubstituted or substituted by one ormore halogen, OR₁₆, COOR₁₆, SR₁₇, CONR₁₈R₁₉; or R₉, R₁₁ and R₁₃independently of each other are C₁-C₂₀alkyl which is unsubstituted orsubstituted by one or more halogen, OR₁₆, SR₁₇, COOR₁₆, CONR₁₈R₁₉,NR₁₈R₁₉, phenyl, C₃-C₈-cycloalkyl, C₃-C₂₀heteroaryl or M; provided thatR₉ and R₁₃ are neither hydrogen nor fluorine.

Or R₁₀ and R₁₂ for example in particular are hydrogen and R₉, R₁₁ andR₁₃ independently of each other are hydrogen, OR₁₆, SR₁₇, NR₁₈R₁₉ orC₂-C₂₀alkyl which is interrupted by one or more O or NR₂₁, wherein theinterrupted C₂-C₂₀alkyl is unsubstituted or substituted by one or morehalogen, OR₁₆, COOR₁₆ or CONR₁₈R₁₉; or R₉, R₁₁ and R₁₃ independently ofeach other are C₁-C₂₀alkyl which is unsubstituted or substituted by oneor more halogen, OR₁₆, SR₁₇, COOR₁₆, CONR₁₈R₁₉, NR₁₈R₁₉, phenyl,C₃-C₈-cycloalkyl or M; provided that R₉ and R₁₃ are no hydrogen.

Or R₁₀ and R₁₂ for example in particular are hydrogen and R₉, R₁₁ andR₁₃ independently of each other are, OR₁₆, SR₁₇, NR₁₈R₁₉ or C₂-C₂₀alkylwhich is interrupted by one or more O, S or NR₂₁, wherein theinterrupted C₂-C₂₀alkyl is unsubstituted or substituted by one or morehalogen, OR₁₆, COOR₁₆, SR₁₇, CONR₁₈R₁₉; or R₉, R₁₁ and R₁₃ independentlyof each other are C₁-C₂₀alkyl which is unsubstituted or substituted byone or more halogen, OR₁₆, SR₁₇, COOR₁₆, CONR₁₈R₁₉, NR₁₈R₁₉, phenyl,C₃-C₈-cycloalkyl, C₃-C₂₀heteroaryl or M.

Or R₁₀ and R₁₂ for example in particular are hydrogen and R₉, R₁₁ andR₁₃ independently of each other are hydrogen, phenyl, halogen,C₁-C₄haloalkyl, CN, NO₂, OR₁₆, SR₁₇, NR₁₈R₁₉, C₁-C₂₀alkyl or C₁-C₂₀alkylwhich is interrupted by one or more O, S, or NR₂₁, provided that R₉ andR₁₃ are neither hydrogen nor fluorine.

In particular R₁₀ and R₁₂ are hydrogen and R₉, R₁₁ and R₁₃ independentlyof each other are hydrogen or C₁-C₂₀alkyl, provided that R₉ and R₁₃ areno hydrogen.

Preferably R₁₀ and R₁₂ are hydrogen and R₉, R₁₁ and R₁₃ are C₁-C₂₀alkyl.

R₁₄ is for example C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which isunsubstituted or substituted by one or more phenyl, C₁-C₄haloalkyl, CN,NO₂, OR₁₆, SR₁₇, NR₁₈R₁₉, PO(OC_(k)H_(2k+1))₂, SO—C₁-C₁₀alkyl,SO₂—C₁-C₁₀alkyl, M,

or by C₂-C₂₀alkyl which is interrupted by one or more O, CO, S, C(O)O,OC(O), phenylene, naphthylene or by NR₂₁, or each of which C₆-C₂₀aryl orC₃-C₂₀heteroaryl is substituted by one or more C₁-C₂₀alkyl which isunsubstituted or substituted by one or more halogen, COOR₁₆, CONR₁₈R₁₉,phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇, NR₁₈R₁₉ or by M.

Or R₁₄ is for example C₆-C₂₀aryl, in particular phenyl or naphthyl, orC₃-C₂₀heteroaryl each of which C₆-C₂₀aryl or C₃-C₂₀heteroaryl isunsubstituted or substituted by one or more phenyl, C₁-C₄haloalkyl, CN,NO₂, OR₁₆, SR₁₇, NR₁₈R₁₉, M,

or by C₂-C₂₀alkyl which is interrupted by one or more O, CO, S, C(O)O,OC(O), phenylene, naphthylene or by NR₂₁, or each of which C₆-C₂₀aryl orC₃-C₂₀heteroaryl is substituted by one or more C₁-C₂₀alkyl which isunsubstituted or substituted by one or more OR₁₆, SR₁₇, NR₁₈R₁₉ or by M.

Or R₁₄ is for example C₆-C₂₀aryl, in particular phenyl or naphthyl, eachof which is unsubstituted or substituted by one or more OR₁₆, SR₁₇,NR₁₈R₁₉, or each of which is substituted by one or more C₁-C₂₀alkyl.

Or R₁₄ is for example C₆-C₂₀aryl, in particular phenyl or naphthyl,preferably phenyl, each of which is unsubstituted or substituted by SR₁₇or OR₁₆, in particular by OR₁₆.

R₁₅ is for example hydrogen, C₃-C₈cycloalkyl, C₂-C₅alkenyl,C₁-C₂₀alkoxy, C₁-C₂₀alkyl, phenyl, naphthyl, or C₃-C₂₀heteroaryl.

Or R₁₅ is for example hydrogen, C₃-C₈cycloalkyl, C₂-C₅alkenyl,C₁-C₂₀alkyl or phenyl.

Or R₁₅ is for example C₃-C₈cycloalkyl, C₂-C₅alkenyl, C₁-C₂₀alkyl, inparticular C₃-C₈cycloalkyl or C₁-C₂₀alkyl, preferably C₁-C₂₀alkyl.

R′₁₄ has one of the meanings as given for R₁₄ or is C₁-C₂₀alkyl;including the examples and preferences as given above.

R′₁₅ has one of the meanings as given for R₁₅; including the examplesand preferences as given above.

R″₁₄ for example is C₁-C₂₀alkyl which is unsubstituted or substituted byphenyl or by phenyl which is substituted by one or more halogen orC₁-C₂₀alkyl; or R″₁₄ is C₂-C₂₀alkyl which is interrupted by one or moreO, CO, S, C(O)O, OC(O), phenylene or NR₂₁; or R″₁₄ is CN, CONR₁₈R₁₉,NO₂, C₁-C₄haloalkyl, S(O)_(m)—C₁-C₆alkyl, S(O)_(m)-phenyl; or R″₁₄ isSO₂O-phenyl, C₆-C₂₀aryl which is unsubstituted or substituted by one ormore phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂, OR₁₆, SR₁₇, NR₁₈R₁₉,PO(OC_(k)H_(2k+1))₂, SO—C₁-C₁₀alkyl, SO₂—C₁-C₁₀alkyl, or by C₂-C₂₀alkylwhich is interrupted by one or more O, CO, S, C(O)O, OC(O), phenylene,naphthylene or by NR₂₁, or each of which is substituted by one or moreC₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, COOR₁₆, CONR₁₈R₁₉, phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl,C₆-C₂₀aryloxycarbonyl, C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇ or byNR₁₈R₁₉.

Or R″₁₄ for example is C₁-C₂₀alkyl which is unsubstituted or substitutedby phenyl; or R″₁₄ is C₂-C₂₀alkyl which is interrupted by one or more O,CO, S, C(O)O, OC(O), phenylene or NR₂₁; or R″₁₄ is C₆-C₂₀aryl, inparticular phenyl or naphthyl, each of which is unsubstituted orsubstituted by one or more OR₁₆, SR₁₇, NR₁₈R₁₉, or each of which issubstituted by one or more C₁-C₂₀alkyl.

In particular R″₁₄ is C₁-C₂₀alkyl which is unsubstituted or substitutedby phenyl; preferably R″₁₄ is C₁-C₂₀alkyl.

M is of the formula (X), (Y) or (Z) as defined above; in particular M isof the formula (X) or (Z), especially (X).

R₁₆ for example is hydrogen, phenyl-C₁-C₃alkyl, C₁-C₂₀alkyl which isunsubstituted or substituted by one or more halogen, OH, SH, CN,OCH₂CH₂(CO)O(C₁-C₄alkyl), O(CO)—(C₁-C₄alkyl), O(CO)-phenyl, (CO)OH,(CO)O(C₁-C₄alkyl), C₃-C₂₀cycloalkyl, O(C₁-C₂₀arylene)-M, or byC₃-C₂₀cycloalkyl which is interrupted by one or more O; or R₁₆ isC₂-C₂₀alkyl which is interrupted by one or more O, S or NR₂₁; or R₁₆ isC₁-C₈alkanoyl, C₂-C₁₂alkenyl, C₃-C₆alkenoyl or C₃-C₂₀cycloalkyl; or R₁₆is C₁-C₈alkyl-C₃-C₁₀cycloalkyl which is uninterrupted or interrupted byone or more O; or R₁₆ is benzoyl; or R₁₆ is phenyl, naphthyl orC₃-C₂₀heteroaryl, in particular phenyl, each of which phenyl, naphthylor C₃-C₂₀heteroaryl is unsubstituted or substituted by one or morehalogen, OH, C₁-C₁₂alkyl, C₁-C₁₂alkoxy, CN, NO₂, phenoxy,C₁-C₁₂alkylsulfanyl, phenylsulfanyl, N(C₁-C₁₂alkyl)₂, diphenylamino or

Or R₁₆ for example is phenyl-C₁-C₃alkyl, C₁-C₂₀alkyl which isunsubstituted or substituted by one or more halogen, OH, SH, CN,C₃-C₂₀cycloalkyl, O(C₁-C₂₀arylene)-M, or by C₃-C₂₀cycloalkyl which isinterrupted by one or more O; or R₁₆ is C₂-C₂₀alkyl which is interruptedby one or more O, S or NR₂₁; or R₁₆ is phenyl or naphthyl, in particularphenyl, each of which is unsubstituted or substituted by one or morehalogen, OH, C₁-C₁₂alkyl, C₁-C₁₂alkoxy, CN, NO₂, N(C₁-C₁₂alkyl)₂,diphenylamino or

In particular R₁₆ is C₁-C₂₀alkyl which is unsubstituted or substitutedby one or more halogen, O(C₁-C₄alkyl), O(CO)—(C₁-C₄alkyl), orO(C₁-C₂₀arylene)-M.

In particular R₁₆ is C₁-C₂₀alkyl which is unsubstituted or substitutedby one or more halogen, O(C₁-C₄alkyl) or O(CO)—(C₁-C₄alkyl). PreferablyR₁₆ is C₁-C₂₀alkyl.

R₁₇ for example is C₂-C₁₂alkenyl, C₃-C₂₀cycloalkyl, phenyl-C₁-C₃alkyl orC₁-C₂₀alkyl; or R₁₇ is C₂-C₂₀alkyl which is interrupted by one or moreO, S, CO, NR₂₁ or COOR₁₆; or R₁₇ is phenyl, naphthyl orC₃-C₂₀heteroaryl, in particular phenyl, each of which is unsubstitutedor substituted by one or more halogen, C₁-C₁₂alkyl, C₁-C₄haloalkyl,C₁-C₁₂alkoxy, CN, NO₂, phenyl-C₁-C₃alkyloxy, phenoxy,C₁-C₁₂alkylsulfanyl, phenylsulfanyl, N(C₁-C₁₂alkyl)₂, diphenylamino,(CO)O(C₁-C₈alkyl), (CO)—C₁-C₈alkyl, (CO)N(C₁-C₈alkyl)₂ or

Or R₁₇ for example is C₂-C₁₂alkenyl, C₃-C₂₀cycloalkyl, phenyl-C₁-C₃alkylor C₁-C₂₀alkyl; or R₁₇ is C₂-C₂₀alkyl which is interrupted by one ormore O, S, CO, NR₂₁ or COOR₁₆; or R₁₇ is phenyl or naphthyl, inparticular phenyl, each of which is unsubstituted or substituted by oneor more halogen, C₁-C₁₂alkyl or

In particular R₁₇ is C₁-C₂₀alkyl which is unsubstituted or substitutedby COOR₁₆.

R₁₈ and R₁₉ for example are independently of each other are hydrogen,C₁-C₂₀alkyl, C₂-C₄hydroxyalkyl, C₂-C₁₀alkoxyalkyl, C₂-C₅alkenyl,C₃-C₂₀cycloalkyl, phenyl-C₁-C₃alkyl, C₁-C₈alkanoyl, C₁-C₈alkanoyloxy,C₃-C₁₂alkenoyl or benzoyl; or R₁₈ and R₁₉ are phenyl, naphthyl orC₃-C₂₀heteroaryl, in particular phenyl, each of which is unsubstitutedor substituted by one or more halogen, C₁-C₄haloalkyl, C₁-C₂₀alkoxy,C₁-C₁₂alkyl, benzoyl or C₁-C₁₂alkoxy; or R₁₈ and R₁₉ together with theN-atom to which they are attached form a 5- or 6-membered saturated orunsaturated ring which is uninterrupted or is interrupted by O or NR₂₁;or R₁₈ and R₁₉ together with the N-atom to which they are attached forma group

Or R₁₈ and R₁₉ for example are independently of each other are hydrogen,C₁-C₂₀alkyl or C₂-C₄hydroxyalkyl; or are phenyl which is unsubstitutedor substituted by one or more halogen or C₁-C₁₂alkyl; or R₁₈ and R₁₉together with the N-atom to which they are attached form a morpholinoring; or R₁₈ and R₁₉ together with the N-atom to which they are attachedform a group

In particular R₁₈ and R₁₉ together with the N-atom to which they areattached form a group

In particular R₁₈ and R₁₉ together with the N-atom to which they areattached form a morpholino ring.

R₂₀ is for example C₁-C₂₀alkyl which is unsubstituted or substituted byone or more halogen, OR₁₆, SR₁₇, COOR₁₆, CONR₁₈R₁₉, NR₁₈R₁₉ or M; or isC₂-C₂₀alkyl which is interrupted by one or more O, CO, C(O)O, OC(O)phenylene or NR₂₁, wherein the interrupted C₂-C₂₀alkyl is unsubstitutedor substituted by one or more halogen, OR₁₆, SR₁₇, COOR₁₆, CONR₁₈R₁₉,NR₁₈R₁₉ or M; or is phenyl, naphthyl or C₃-C₂₀heteroaryl, in particularthienyl, each of which phenyl, naphthyl or C₃-C₂₀heteroaryl isunsubstituted or substituted by one or more halogen, C₁-C₄haloalkyl, CN,NO₂, OR₁₆, SR₁₇, NR₁₈R₁₉, M,

or by C₂-C₂₀alkyl which is interrupted by one or more O, S, or NR₂₁, oreach of which is substituted by one or more C₁-C₂₀alkyl which isunsubstituted or substituted by one or more halogen, COOR₁₆, phenyl,C₃-C₈cycloalkyl, OR₁₆, SR₁₇ or NR₁₈R₁₉.

Or R₂₀ is for example C₁-C₂₀alkyl which is unsubstituted or substitutedby one or more halogen, OR₁₆, SR₁₇, NR₁₈R₁₉, or M; or is C₂-C₂₀alkylwhich is interrupted by one or more O, CO, C(O)O, OC(O), phenylene orNR₂₁, wherein the interrupted C₁-C₂₀alkyl is unsubstituted orsubstituted by one or more halogen, OR₁₆, COOR₁₆, NR₁₈R₁₉ or M;

or is phenyl, naphthyl or C₃-C₂₀heteroaryl, in particular thienyl, eachof which phenyl, naphthyl or C₃-C₂₀heteroaryl is unsubstituted orsubstituted by one or more halogen, C₁-C₄haloalkyl, CN, NO₂, OR₁₆,NR₁₈R₁₉,

or by C₁-C₂₀alkyl which is interrupted by one or more O, S, or NR₂₁, oreach of which is substituted by one or more C₁-C₂₀alkyl.

Or R₂₀ is for example C₁-C₂₀alkyl which is unsubstituted or substitutedby one or more NR₁₈R₁₉; or is C₂-C₂₀alkyl which is interrupted by one ormore C(O)O, OC(O) or phenylene, wherein the interrupted C₁-C₂₀alkyl isunsubstituted or substituted by NR₁₈R₁₉; or is phenyl, naphthyl orC₃-C₂₀heteroaryl, in particular thienyl, each of which phenyl, naphthylor C₃-C₂₀heteroaryl is unsubstituted or substituted by

Or R₂₀ is for example unsubstituted C₁-C₂₀alkyl or C₂-C₂₀alkyl which isinterrupted by one or more C(O)O, OC(O) and which interruptedC₂-C₂₀alkyl is substituted by NR₁₈R₁₉, or R₂₀ is phenyl or thienyl, bothof which are unsubstituted or substituted by

Or R₂₀ is for example C₁-C₂₀alkyl, phenyl or C₃-C₂₀heteroaryl, inparticular thienyl, each of which is unsubstituted or substituted by

Preferably R₂₀ is C₁-C₂₀alkyl, phenyl, or phenyl which is substituted by

In particular R₂₀ is C₁-C₂₀alkyl.

R₂₁ for example is hydrogen, C₁-C₂₀alkyl, C₁-C₄haloalkyl, (CO)R₄₁,C₂-C₂₀alkyl which is interrupted by one or more O, CO, C(O)O or OC(CO),or is phenyl-C₁-C₄alkyl, C₃-C₈cycloalkyl; or R₂₁ is phenyl or naphthylboth of which are unsubstituted or substituted by one or moreC₁-C₂₀alkyl, halogen, C₁-C₄haloalkyl, OR₁₆, SR₁₇, NR₁₈R₁₉ or

Or R₂₁ for example is C₁-C₂₀alkyl, C₁-C₄haloalkyl, phenyl-C₁-C₄alkyl,C₃-C₈cycloalkyl or phenyl which is unsubstituted or substituted by oneor more C₁-C₂₀alkyl.

In particular R₂₁ is C₁-C₂₀alkyl.

R₂₂, R₂₃, R₂₄, R₂₅, R₂₆ or R₂₇ for example independently of each otherare hydrogen, COR₄₁ or

or one of R₂₂, R₂₃ or R₂₄ and one of R₂₅, R₂₆ or R₂₇ together with X₃and the phenyl rings to which they are attached form a heteroaromaticring system.

Or R₂₂, R₂₃, R₂₄, R₂₅, R₂₆ or R₂₇ for example independently of eachother are hydrogen, NO₂ or

or one of R₂₂, R₂₃ or R₂₄ and one of R₂₅, R₂₆ or R₂₇ together with X₃and the phenyl rings to which they are attached form a heteroaromaticring system.

Or R₂₂, R₂₃, R₂₄, R₂₅, R₂₆ or R₂₇ for example independently of eachother are hydrogen or one of R₂₂, R₂₃ or R₂₄ and one of R₂₅, R₂₆ or R₂₇together with X₃ and the phenyl rings to which they are attached form aheteroaromatic ring system.

Or R₂₂, R₂₃, R₂₄, R₂₅, R₂₆ or R₂₇ for example independently of eachother are hydrogen, COR₄₁, NO₂ or

R₃₁ and R₃₂ for example independently of each other are C₁-C₂₀alkyl; orR₃₁ and R₃₂ together with N-atom to which they are attached form amorpholino ring.

R₃₃, R₃₄, R₃₅, R₃₆, R₃₇, R₃₈, R₃₉ and R₄₀ for example independently ofeach other are hydrogen,

NO₂, COR₁₆, C₁-C₂₀alkyl, C₁-C₄haloalkyl, OR₁₆, SR₁₇, NR₁₈R₁₉, halogen,CN, phenyl or C₃-C₂₀cycloalkyl; or R₃₅ and R₃₆ or R₃₇ and R₃₈ or both,R₃₅ and R₃₆ and R₃₇ and R₃₈ are

Or R₃₃, R₃₄, R₃₅, R₃₆, R₃₇, R₃₈, R₃₉ and R₄₀ for example independentlyof each other are hydrogen,

NO₂ or COR₁₆; or R₃₅ and R₃₆ or R₃₇ and R₃₈ or both, R₃₅ and R₃₆ and R₃₇and R₃₈ are

Or R₃₃, R₃₄, R₃₅, R₃₆, R₃₇, R₃₈, R₃₉ and R₄₀ for example independentlyof each other are hydrogen,

NO₂ or COR₁₆; or R₃₅ and R₃₆ or R₃₇ and R₃₈ or both, are

Or for example R₃₃, R₃₅, R₃₆, R₃₇, R₃₈, R₃₉ and R₄₀ for exampleindependently of each other are hydrogen or

and R₃₄ is NO₂ or COR₁₆; or R₃₅ and R₃₆ or R₃₆ and R₃₇ are

In particular R₃₃, R₃₄, R₃₅, R₃₆, R₃₇, R₃₈, R₃₉ and R₄₀ for exampleindependently of each other are hydrogen or

Preferably R₃₃, R₃₄, R₃₅, R₃₆, R₃₈, R₃₉ and R₄₀ are hydrogen and R₃₇ is

R₄₁ for example is C₆-C₂₀aryl, in particular phenyl, or C₃-C₂₀heteroaryleach of which is unsubstituted or substituted by one or more phenyl,C₁-C₄haloalkyl, OR₁₆, SR₁₇, NR₁₈R₁₉ or by C₂-C₂₀alkyl which isinterrupted by one or more O, or each of which C₆-C₂₀aryl orC₃-C₂₀heteroaryl is substituted by one or more C₁-C₂₀alkyl which isunsubstituted or substituted by one or more COOR₁₆, CONR₁₈R₁₉, phenyl,C₃-C₈cycloalkyl, C₆-C₂₀aryloxycarbonyl, OR₁₆, SR₁₇ or NR₁₈R₁₉; or R₄₁ is

hydrogen, OH, C₁-C₂₀alkyl, C₁-C₄haloalkyl, C₂-C₂₀alkyl which isinterrupted by one or more O, CO or NR₂₁, or R₄₁ is C₃-C₂₀cycloalkylwhich is uninterrupted or is interrupted by O, S, CO or NR₂₁.

Or R₄₁ for example is phenyl which is unsubstituted or substituted byone or more OR₁₆, SR₁₇, NR₁₈R₁₉ or by C₁-C₂₀alkyl; or R₄₁ is

hydrogen, OH, C₁-C₂₀alkyl, C₁-C₄haloalkyl, C₂-C₂₀alkyl which isinterrupted by one or more O, CO or NR₂₁, or R₄₁ is C₃-C₂₀cycloalkylwhich is uninterrupted or is interrupted by O, S, CO or NR₂₁.

Or R₄₁ for example is

hydrogen, OH, C₁-C₂₀alkyl, C₁-C₄haloalkyl, C₂-C₂₀alkyl which isinterrupted by one or more O, CO or NR₂₁, or R₄₁ is C₃-C₂₀cycloalkylwhich is uninterrupted or is interrupted by O, S, CO or NR₂₁.

Or R₄₁ for example is hydrogen, OH, C₁-C₂₀alkyl, C₁-C₄haloalkyl,C₂-C₂₀alkyl which is interrupted by one or more O, CO or NR₂₁, or R₄₁ isC₃-C₂₀cycloalkyl which is uninterrupted or is interrupted by O, S, CO orNR₂₁.

In particular R₄₁ is phenyl which is substituted by C₁-C₂₀alkyl.

n is an integer 1-20, for example 1-12, 1-10, 1-8, 1-4, 1-3 or 1 or 2.

m is an integer 1 or 2; or for example is an integer 1 or for example isan integer 2.

k is an integer 1-10, for example 1-8, 1-4, or 1 or 2.

Z is for example

Z is for example C₄-C₂₀heteroaroyl which is unsubstituted or substitutedby one or more identical or different R₁₀, in particular unsubstitutedC₄-C₂₀heteroaroyl.

Z preferably is

The two groups Z₁ in the compounds of the formula II and III areidentical or different.

Z₁ for example is NO₂, C₇-C₂₀aroyl or C₃-C₂₀heteroaroyl, whereC₆-C₁₈aroyl or C₄-C₂₀heteroaroyl is unsubstituted or substituted by oneor more identical or different R₁₀; provided that at least one Z₁ isother than NO₂.

Z₁ for example is NO₂ or C₇-C₂₀aroyl, which is unsubstituted orsubstituted by one or more identical or different R₁₀.

Z₁ for example is NO₂ or C₃-C₂₀heteroaroyl, which is unsubstituted orsubstituted by one or more identical or different R₁₀.

Z₁ for example is C₇-C₂₀aroyl or C₃-C₂₀heteroaroyl, where C₆-C₁₈aroyl orC₄-C₂₀heteroaroyl is unsubstituted or substituted by one or moreidentical or different R₁₀.

Z₁ in particular is C₇-C₂₀aroyl.

Z₂ is for example C₇-C₂₀aroyl or C₄-C₂₀heteroaroyl, where C₇-C₁₈aroyl orC₄-C₂₀heteroaroyl are unsubstituted or substituted by one or moreidentical or different R₁₀.

Z₂ is for example C₇-C₂₀aroyl or C₄-C₂₀heteroaroyl, in particularC₇-C₂₀aroyl.

Q₃ is for example phenylene, naphthylene or C₃-C₁₂heteroarylene, all ofwhich are substituted by

Q₃ is for example

preferably

Preferred are compounds of the formula I, II, III or IV, in particularthe compounds of the formula I.

Interesting are compounds of the formula I as defined above, wherein

R₁, R₂, R₃, R₄, R₅ and R₆ independently of each other are hydrogen,OR₁₆, or C₁-C₂₀alkyl which is unsubstituted or substituted by one ormore halogen, OR₁₆, COOR₁₆, CONR₁₈R₁₉, NR₁₈R₁₉;R₉, R₁₀, R₁₁, R₁₂ and R₁₃ independently of each other are hydrogen,halogen, OR₁₆, SR₁₇, NR₁₈R₁₉ or C₁-C₂₀alkyl which is interrupted by oneor more O, S, NR₂₁, or independently each of which R₉, R₁₀, R₁₁, R₁₂ andR₁₃ is C₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, OR₁₆, SR₁₇, COOR₁₆, CONR₁₈R₁₉, NR₁₈R₁₉, phenyl,C₃-C₉-cycloalkyl or C₃-C₂₀heteroaryl;provided that R₉ and R₁₃ is neither hydrogen nor fluorine;R₁₄ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstituted orsubstituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₆, SR₁₇, NR₁₈R₁₉, PO(OC_(k)H_(2k+1))₂, SO—C₁-C₁₀alkyl,SO₂—C₁-C₁₀alkyl, M,

or by C₂-C₂₀alkyl which is interrupted by one or more O, CO, S, C(O)O,OC(O), phenylene, naphthylene or by NR₂₁, or each of which issubstituted by one or more C₁-C₂₀alkyl which is unsubstituted orsubstituted by one or more halogen, COOR₁₆, CONR₁₈R₁₉, phenyl,C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇, NR₁₈R₁₉ or by M;

M is

R″₁₄ is C₁-C₂₀alkyl which is unsubstituted or substituted by phenyl orby phenyl which is substituted by halogen, C₁-C₂₀alkyl, C₁-C₄haloalkyl,OR₁₆, SR₁₇ or by NR₁₈R₁₉;or R″₁₄ is C₂-C₂₀alkyl which is interrupted by one or more O, CO, S,C(O)O, OC(O), phenylene, naphthylene or NR₂₁, wherein the interruptedC₂-C₂₀alkyl is unsubstituted or substituted by one or more halogen,OR₁₆, COOR₁₆, CONR₁₈R₁₉, phenyl, or by phenyl which is substituted byOR₁₆, SR₁₇ or NR₁₈R₁₉;or R″₁₄ is CN, CONR₁₈R₁₉, NO₂, C₁-C₄haloalkyl;R₁₅ is C₁-C₂₀alkyl, phenyl, or C₁-C₈alkoxy;k is an integer 1-10;R′₁₄ has one of the meanings as given for R₁₄;R′₁₅ has one of the meanings as given for R₁₅;X₁ is O, CO, S or a direct bond;

X₃ is O, S or NR′₂₀;

R₁₆ is hydrogen, phenyl-C₁-C₃alkyl, C₁-C₂₀alkyl which is unsubstitutedor substituted by one or more halogen, OCH₂CH₂CN,OCH₂CH₂(CO)O(C₁-C₄alkyl), O(CO)—(C₁-C₄alkyl), O(CO)—(C₂-C₄)alkenyl,O(CO)-phenyl, (CO)O H, (CO)O(C₁-C₄alkyl), C₃-C₂₀cycloalkyl,SO₂—(C₁-C₄haloalkyl), O(C₁-C₄haloalkyl), O(C₁-C₂₀arylene)-M or byC₃-C₂₀cycloalkyl which is interrupted by one or more O;or R₁₆ is C₂-C₂₀alkyl which is interrupted by one or more O, S or NR₂₁;R₁₇ is methyl substituted by COOR₁₆;or R₁₇ is phenyl unsubstituted or substituted by one or moreC₁-C₁₂alkyl, C₁-C₁₂alkoxy, or

R₁₈ and R₁₉ independently of each other are hydrogen, phenyl,C₁-C₂₀alkyl, C₁-C₈alkanoyl or C₁-C₈alkanoyloxy;or R₁₈ and R₁₉ together with the N-atom to which they are attached forma heteroaromatic ring system which is unsubstituted or substituted by

or R₁₈ and R₁₉ together with the N-atom to which they are attached forma group

R₂₀ is hydrogen, C₁-C₄haloalkyl, or C₁-C₂₀alkyl which is unsubstitutedor substituted by one or more halogen, OR₁₆, SR₁₇, COOR₁₆, CONR₁₇R₁₈,NR₁₇R₁₈, PO(OC_(k)H_(2k+1))₂ or M;or R₂₀ is C₂-C₂₀alkyl of which is interrupted by one or more O, CO,C(O)O, OC(O) or NR₂₁, wherein the interrupted C₂-C₂₀alkyl isunsubstituted or substituted by one or more halogen, OR₁₆, SR₁₇, COOR₁₆,CONR₁₈R₁₉, NR₁₈R₁₉ or M;or R₂₀ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which are unsubstitutedor substituted by one or more halogen, C₁-C₄haloalkyl, OR₁₆, SR₁₇,NR₁₈R₁₉, or

or by C₂-C₂₀alkyl which is interrupted by one or more O, S or NR₂₁, oreach of which C₆-C₂₀aryl or C₃-C₂₀heteroaryl is substituted by one ormore C₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, COOR₁₆, CONR₁₈R₁₉, phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl,C₆-C₂₀aryloxycarbonyl, C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇ orNR₁₈R₁₉;R₂₁ is hydrogen, C₁-C₂₀alkyl or C₂-C₂₀alkyl which is interrupted by oneor more O or CO;or R₂₁ is phenyl or naphthyl both of which are unsubstituted orsubstituted by one or more C₁-C₂₀alkyl, halogen, C₁-C₄haloalkyl, OR₁₆,SR₁₇, NR₁₈R₁₉, COR₄₁ or

R₂₂, R₂₃, R₂₄, R₂₅, R₂₆, or R₂₇ independently of each other is hydrogen,COR₄₁, NO₂ or

or one of R₂₂ and R₂₃, R₂₄ and R₂₅, or R₂₆ and R₂₇ is

or one of R₂₂, R₂₃ or R₂₄ and one of R₂₅, R₂₆ or R₂₇ together with X₃and the phenyl rings to which they are attached form a heteroaromaticring system which is unsubstituted or substituted by one or moreC₁-C₂₀alkyl, C₁-C₂₀alkoxy, OR₁₆, SR₁₇, NR₁₈R₁₉, COR₄₁,

NO₂ or phenyl;R₂₈ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstituted orsubstituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₆, SR₁₇, NR₁₈R₁₉ or by C₁-C₂₀alkyl which is interrupted by one ormore O, S, or NR₂₁, or each of which C₆-C₂₀aryl or C₃-C₂₀heteroaryl issubstituted by one or more C₁-C₂₀alkyl which is unsubstituted orsubstituted by one or more halogen, COOR₁₆, CONR₁₈R₁₉, phenyl,C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇ or NR₁₈R₁₉;R₃₃, R₃₄, R₃₅, R₃₆, R₃₇, R₃₈, R₃₉ and R₄₀ independently of each otherare hydrogen,

NO₂, COR₄₁, C₁-C₂₀alkyl, C₁-C₄haloalkyl, OR₁₆, SR₁₇, NR₁₈R₁₉, halogen,CN, phenyl or C₃-C₂₀cycloalkyl which is uninterrupted or is interruptedby one or more O, S, CO or NR₂₁;or R₃₅ and R₃₆ or R₃₇ and R₃₈ or both, R₃₅ and R₃₆ and R₃₇ and R₃₈ are

R₄₁ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstituted orsubstituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₆, SR₁₇, NR₁₈R₁₉ or by C₁-C₂₀alkyl which is interrupted by one ormore O, S, or NR₂₁, or each of which C₆-C₂₀aryl or C₃-C₂₀heteroaryl issubstituted by one or more C₁-C₂₀alkyl which is unsubstituted orsubstituted by one or more halogen, COOR₁₆, CONR₁₈R₁₉, phenyl,C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇ or NR₁₈R₁₉;

or R₄₁ is

or R₄₁ is hydrogen, OH, C₁-C₂₀alkyl, C₁-C₄haloalkyl, C₂-C₂₀alkyl whichis interrupted by one or more O, CO or by NR₂₁, or is C₃-C₂₀cycloalkylwhich is uninterrupted or is interrupted by O, S, CO or NR₂₁.

Further interesting are compounds of the formula I as defined above,wherein R₉, R₁₁ and R₁₃ are methyl and R₁₀ and R₁₂ are hydrogen.

Interesting are compounds of the formula I according to claim 1, wherein

R₁, R₂, R₃, R₄, R₅ and R₆ are hydrogen;R₉, R₁₀, R₁₁, R₁₂ and R₁₃ independently of each other are hydrogen, orC₁-C₂₀alkyl;provided that R₉ and R₁₃ are neither hydrogen nor fluorine;R₁₄ is C₆-C₂₀aryl which is unsubstituted or substituted by OR₁₆, or byC₁-C₂₀alkyl which is unsubstituted or substituted by SR₁₇;

M is

R₁₅ is C₁-C₂₀alkyl;R′₁₄ is C₁-C₂₀alkyl or C₆-C₂₀aryl;R′₁₅ is C₁-C₂₀alkyl;X₁ is a direct bond;

X₃ is NR′₂₀,

R₁₆ is C₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, or O(C₁-C₂₀arylene)-M;R₁₇ is C₁-C₂₀alkyl which is unsubstituted or substituted by COOR₁₆;R₁₈ and R₁₉ together with the N-atom to which they are attached form agroup

R₂₀ is C₁-C₂₀alkyl;or R₂₀ is C₂-C₂₀alkyl of which is interrupted by one or more C(O)O orOC(O) wherein the interrupted C₂-C₂₀alkyl is unsubstituted orsubstituted by NR₁₈R₁₉;or R₂₀ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstitutedor substituted by

R′₂₀ is C₁-C₂₀alkyl;R₂₂, R₂₃, R₂₄, R₂₅, R₂₆ or R₂₇ independently of each other are hydrogen,or R₂₂ and R₂₅ together with X₃ and the phenyl rings to which they areattached form a heteroaromatic ring system;R₂₈ is C₆-C₂₀aryl which is unsubstituted or substituted by C₁-C₂₀alkyl;R₃₃, R₃₄, R₃₅, R₃₆, R₃₇, R₃₈, R₃₉ and R₄₀ independently of each otherare hydrogen, or COR₄₁;

R₄₁ is C₆-C₂₀aryl which is unsubstituted or substituted by C₁-C₂₀alkyl.

Of interest are compounds of the formula I as described above, wherein

Z is

R₁, R₂, R₃, R₄, R₅ and R₆ are hydrogen;R₁₀ and R₁₂ are hydrogen;R₁₁ is hydrogen, OR₁₆ or C₁-C₂₀alkyl;R₉ and R₁₃ independently of each other are OR₁₆ or C₁-C₂₀alkyl;R₁₄ is C₆-C₂₀aryl which is unsubstituted or substituted by one or moreNO₂, SR₁₇,

NR₁₈R₁₉ or C₁-C₂₀alkyl;

M is

G is —COR₂₈;

R₁₅ is C₁-C₂₀alkyl;R′₁₄ has one of the meanings as given for R₁₄;R′₁₅ has one of the meanings as given for R₁₅;R₁₆ is C₁-C₂₀alkyl, which is unsubstituted or substituted by one or morehalogen, OH, O(C₁-C₄alkyl), O(CO)—(C₁-C₄alkyl) or O(C₁-C₂₀arylene)-M,or R₁₆ is C₁-C₈alkanoyl;

R₁₇ is COOR₁₆;

R₁₈ and R₁₉ independently of each other are C₁-C₂₀alkyl,or R₁₈ and R₁₉ together with the N-atom to which they are attached forma 5- or 6-membered saturated or unsaturated ring which is uninterruptedor is interrupted by O, or R₁₈ and R₁₉ together with the N-atom to whichthey are attached form a group

R₂₀ is C₁-C₂₀alkyl or C₂-C₂₀alkyl of which is interrupted by one or moreO, wherein the interrupted C₂-C₂₀alkyl is unsubstituted or substitutedby NR₁₈R₁₉;or R₂₀ is C₆-C₂₀aryl which is substituted by

R₂₂, R₂₃, R₂₅ and R₂₆ are hydrogen,R₂₄ and R₂₇ together with X₃ and the phenyl rings to which they areattached form a heteroaromatic ring system;R₂₈ is C₆-C₂₀aryl which is unsubstituted or substituted by C₁-C₂₀alkyl;R₃₃, R₃₅, R₃₆, R₃₇, R₃₈ and R₄₀ independently of each other arehydrogen;

R₃₄ is

R₃₉ is COR₄₁;

R₄₁ is C₆-C₂₀aryl which is unsubstituted or substituted by C₁-C₂₀alkyl.

Preferred are compounds of the formula I, II, III or IV as definedabove, wherein

Z is

Z₁ is C₇-C₂₀aroyl, which is unsubstituted or substituted by one or moreidentical or different R₁₀;R₁, R₂, R₃, R₄, R₅ and R₆ are hydrogen;R₁₀ and R₁₂ are hydrogen;R₁₁ is hydrogen, OR₁₆ or C₁-C₂₀alkyl;R₉ and R₁₃ independently of each other are OR₁₆ or C₁-C₂₀alkyl;R₁₄ is C₆-C₂₀aryl which is unsubstituted or substituted by one or moreNO₂, OR₁₆, NR₁₈R₁₉ or C₁-C₂₀alkyl which C₁-C₂₀alkyl is unsubstituted orsubstituted by SR₁₇;Q is C₆-C₂₀arylene;Q₁ is C₁-C₂₀alkylene;

Q₂ is

where the double asterix denotes the bond to the carbazyl group;

M is

G is —COR₂₈;

L is O—C₁-C₂₀alkylene-O, O—C₂-C₂₀alkylene-O which is interrupted by oneor more O;R″₁₄ is C₁-C₂₀alkyl or C₆-C₂₀aryl which C₆-C₂₀aryl is unsubstituted orsubstituted by C₁-C₂₀alkyl;R₁₅ is C₁-C₂₀alkyl;R′₁₄ is C₁-C₂₀alkyl;R′₁₅ is C₁-C₂₀alkyl;X₃ together with R₂₄ and R₂₇ and the phenyl rings to which they areattached forms a heteroaromatic ring system;R₁₆ is C₁-C₂₀alkyl, which is unsubstituted or substituted by one or morehalogen, OH, O(C₁-C₄alkyl), O(CO)—(C₁-C₄alkyl) or O(C₁-C₂₀arylene)-M;or R₁₆ is C₂-C₂₀alkyl which is interrupted by one or more O, whichinterrupted C₂-C₂₀alkyl is substituted by O—C₆-C₂₀arylene-M, in whichO—C₆-C₂₀arylene-M, the arylene is unsubstituted or substituted byO(C₁-C₆alkyl);or R₁₆ is C₁-C₈alkanoyl;R₁₇ is C₁-C₂₀alkyl which is unsubstituted or substituted by COOR₁₆;R₁₈ and R₁₉ independently of each other are C₁-C₂₀alkyl,or R₁₈ and R₁₉ together with the N-atom to which they are attached forma 5- or 6-membered saturated or unsaturated ring which is uninterruptedor is interrupted by O, or R₁₈ and R₁₉ together with the N-atom to whichthey are attached form a group

R₂₀ is C₁-C₂₀alkyl or C₂-C₂₀alkyl of which is interrupted by one or moreO, wherein the interrupted C₂-C₂₀alkyl is unsubstituted or substitutedby NR₁₈R₁₉;or R₂₀ is C₆-C₂₀aryl which is substituted by

R₂₂, R₂₃, R₂₅ and R₂₆ are hydrogen,R₂₄ and R₂₇ together with X₃ and the phenyl rings to which they areattached form a heteroaromatic ring system;R₂₈ is C₆-C₂₀aryl which is unsubstituted or substituted by C₁-C₂₀alkyl;R₃₃, R₃₅, R₃₆, R₃₇, R₃₈ and R₄₀ independently of each other arehydrogen;

R₃₄ is

R₃₉ is COR₄₁;

R₄₁ is C₆-C₂₀aryl which is unsubstituted or substituted by C₁-C₂₀alkyl.

Other interesting compounds are compounds of the formula I, II, III or Vas described above, wherein

Z is

Z₁ is C₇-C₂₀aroyl which is unsubstituted or substituted by one or moreidentical or different R₁₀;Z₂ is C₇-C₂₀aroyl which is unsubstituted or substituted by one or moreidentical or different R₁₀;R₁, R₂, R₃, R₄, R₅ and R₆ are hydrogen;R₁₀, R₁₁ and R₁₂ independently of each other are hydrogen, OR₁₆ orC₁-C₂₀alkyl;R₉ and R₁₃ independently of each other are OR₁₆ or C₁-C₂₀alkyl;R₁₄ is C₆-C₂₀aryl which is unsubstituted or substituted by one or moreNO₂, OR₁₆, SR₁₇, NR₁₈R₁₉ or C₁-C₂₀alkyl;Q is C₆-C₂₀arylene;Q₁ is a direct bond;Q₃ is phenylene which is substituted by

M is

L is C₂-C₂₀alkylene which is interrupted by one or more groups O,or L is O—C₁-C₂₀alkylene-O,wherein all radicals L as defined are unsubstituted or substituted byone or more halogen;R″₁₄ is C₆-C₂₀aryl which is unsubstituted or substituted by C₁-C₂₀alkyl;R₁₅ is C₁-C₂₀alkyl;

X₃ is NR′₂₀,

R₁₆ is C₁-C₂₀alkyl, which is unsubstituted or substituted by one or morehalogen, OH, O(C₁-C₄alkyl), O(CO)—(C₁-C₄alkyl),or R₁₆ is C₂-C₂₀alkyl which is interrupted by one or more O, whichinterrupted C₂-C₂₀alkyl is unsubstituted or substituted byO—C₆-C₂₀arylene-M, in which O—C₆-C₂₀arylene-M, the arylene isunsubstituted or substituted by one or more O(C₁-C₆alkyl);R₁₇ is C₁-C₂₀alkyl which is unsubstituted or substituted by COOR₁₆;R₁₈ and R₁₉ independently of each other are C₁-C₂₀alkyl,or R₁₈ and R₁₉ together with the N-atom to which they are attached forma 5- or 6-membered saturated or unsaturated ring which is uninterruptedor is interrupted by O,R₂₀ and R′₂₀ are C₁-C₂₀alkyl;R₂₂, R₂₃, R₂₄, R₂₅, R₂₆ or R₂₇ independently of each other are hydrogen,or one of R₂₂, R₂₃ or R₂₄ and one of R₂₅, R₂₆ or R₂₇ together with X₃and the phenyl rings to which they are attached form a heteroaromaticring system.

Additionally preferred are compounds of the formula I according to claim1, wherein

R₁, R₂, R₃, R₄, R₅ and R₆ are hydrogen;R₉, R₁₁ and R₁₃ are C₁-C₂₀alkyl;R₁₀ and R₁₂ are hydrogen;R₁₄ is C₆-C₂₀aryl which is unsubstituted or substituted by C₁-C₂₀alkylwhich is unsubstituted or substituted by SR₁₇;R₁₅ is C₁-C₂₀alkyl;R₁₆ is C₁-C₂₀alkyl;R₁₇ is C₁-C₂₀alkyl which is unsubstituted or substituted by COOR₁₆; andR₂₀ is C₁-C₂₀alkyl.

Preferred are compounds of the formula I, II, III or IV as definedabove, wherein

Z₁ is C₇-C₂₀aroyl, which is substituted by R₁₀;R″₁₄ is C₁-C₂₀alkyl or C₆-C₂₀aryl which is substituted by C₁-C₂₀alkyl;R₁₆ is C₁-C₂₀alkyl, which is unsubstituted or substituted by one or morehalogen, OH, O(C₁-C₄alkyl), O(CO)—(C₁-C₄alkyl) or O(C₁-C₂₀arylene)-M;or R₁₆ is C₂-C₂₀alkyl which is interrupted by one or more O, whichinterrupted C₂-C₂₀alkyl is substituted by O—C₆-C₂₀arylene-M, in whichO—C₆-C₂₀arylene-M, the arylene is substituted by O(C₁-C₆alkyl);or R₁₆ is C₁-C₈alkanoyl;R₁₇ is C₁-C₂₀alkyl which is substituted by COOR₁₆;R₁₈ and R₁₉ independently of each other are C₁-C₂₀alkyl,or R₁₈ and R₁₉ together with the N-atom to which they are attached forma 6-membered saturated ring which is uninterrupted or is interrupted byO,or R₁₈ and R₁₉ together with the N-atom to which they are attached forma group

R₂₀ is C₁-C₂₀alkyl or C₂-C₂₀alkyl of which is interrupted by one or moreO, wherein the interrupted C₂-C₂₀alkyl is substituted by NR₁₈R₁₉;or R₂₀ is C₆-C₂₀aryl which is substituted by

R₂₄ and R₂₇ together with X₃ and the phenyl rings to which they areattached form a carbazolyl ring system;R₂₈ is C₆-C₂₀aryl which is substituted by C₁-C₂₀alkyl;R₄₁ is C₆-C₂₀aryl which is substituted by C₁-C₂₀alkyl.

The compounds of the formula I, II, III, IV and V are suitable asradical photoinitiators. Accordingly, subject of the invention is theuse of a compound of the formula I, II, III, IV or V as defined abovefor the photopolymerization of a composition comprising at least oneethylenically unsaturated photopolymerizable compound.

Another subject of the present invention therefore is aphotopolymerizable composition comprising

(a) at least one ethylenically unsaturated photopolymerizable compoundand(b) as photoinitiator, at least one compound of the formula I, II, III,IV or V as defined above.

The composition may comprise additionally to the photoinitiator (b) atleast one further photoinitiator (c), and/or other additives (d).

The composition may comprise additionally to the photoinitiator (b) atleast one further photoinitiator (c) or other additives (d) or both, atleast one further photoinitiator (c) and other additives (d).

The unsaturated compounds (a) may include one or more olefinic doublebonds. They may be of low (monomeric) or high (oligomeric) molecularmass. Examples of monomers containing a double bond are alkyl,hydroxyalkyl, cycloalkyl (which optionally interrupted by O) or aminoacrylates, or alkyl, hydroxyalkyl, cycloalkyl (which optionallyinterrupted by O) or amino methacrylates, for example methyl, ethyl,butyl, 2-ethylhexyl or 2-hydroxyethyl acrylate, tetrahydrofurfurylacrylate, isobornyl acrylate, methyl methacrylate, cyclohexylmethacrylate or ethyl methacrylate. Silicone acrylates are alsoadvantageous. Other examples are acrylonitrile, acrylamide,methacrylamide, N-substituted (meth)acrylamides, vinyl esters such asvinyl acetate, vinyl ethers such as isobutyl vinyl ether, styrene,alkyl- and halostyrenes, N-vinylpyrrolidone, vinyl chloride orvinylidene chloride.

Examples of monomers containing two or more double bonds are thediacrylates of ethylene glycol, propylene glycol, neopentyl glycol,hexamethylene glycol or of bisphenol A, and4,4′-bis(2-acryl-oyloxyethoxy)diphenylpropane, trimethylolpropanetriacrylate, pentaerythritol triacrylate or tetraacrylate, vinylacrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallylphosphate, triallyl isocyanurate or tris(2-acryloylethyl) isocyanurate.

Examples of polyunsaturated compounds of relatively high molecular mass(oligomers) are acrylated epoxy resins, polyesters containing acrylate-,vinyl ether- or epoxy-groups, and also polyurethanes and polyethers.Further examples of unsaturated oligomers are unsaturated polyesterresins, which are usually prepared from maleic acid, phthalic acid andone or more diols and have molecular weights of from about 500 to 3000.In addition it is also possible to employ vinyl ether monomers andoligomers, and also maleate-terminated oligomers with polyester,polyurethane, polyether, polyvinyl ether and epoxy main chains. Ofparticular suitability are combinations of oligomers which carry vinylether groups and of polymers as described in WO 90/01512. However,copolymers of vinyl ether and maleic acid-functionalized monomers arealso suitable. Unsaturated oligomers of this kind can also be referredto as prepolymers.

Particularly suitable examples are esters of ethylenically unsaturatedcarboxylic acids and polyols or polyepoxides, and polymers havingethylenically unsaturated groups in the chain or in side groups, forexample unsaturated polyesters, polyamides and polyurethanes andcopolymers thereof, polymers and copolymers containing (meth)acrylicgroups in side chains, and also mixtures of one or more such polymers.

Examples of unsaturated carboxylic acids are acrylic acid, methacrylicacid, crotonic acid, itaconic acid, cinnamic acid, and unsaturated fattyacids such as linolenic acid or oleic acid. Acrylic and methacrylic acidare preferred.

Suitable polyols are aromatic and, in particular, aliphatic andcycloaliphatic polyols. Examples of aromatic polyols are hydroquinone,4,4′-dihydroxydiphenyl, 2,2-di(4-hydroxyphenyl)propane, and alsonovolaks and resols. Examples of polyepoxides are those based on theabovementioned polyols, especially the aromatic polyols, andepichlorohydrin. Other suitable polyols are polymers and copolymerscontaining hydroxyl groups in the polymer chain or in side groups,examples being polyvinyl alcohol and copolymers thereof orpolyhydroxyalkyl methacrylates or copolymers thereof. Further polyolswhich are suitable are oligoesters having hydroxyl end groups.

Examples of aliphatic and cycloaliphatic polyols are alkylenediolshaving preferably 2 to 12 C atoms, such as ethylene glycol, 1,2- or1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, pentanediol, hexanediol,octanediol, dodecanediol, diethylene glycol, triethylene glcyol,polyethylene glycols having molecular weights of preferably from 200 to1500, 1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol,1,4-dihydroxymethylcyclohexane, glycerol, tris(β-hydroxyethyl)amine,trimethylolethane, trimethylolpropane, pentaerythritol,dipentaerythritol and sorbitol.

The polyols may be partially or completely esterified with onecarboxylic acid or with different unsaturated carboxylic acids, and inpartial esters the free hydroxyl groups may be modified, for exampleetherified or esterified with other carboxylic acids.

Examples of esters are:

trimethylolpropane triacrylate, trimethylolethane triacrylate,trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate,tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate,tetraethylene glycol diacrylate, pentaerythritol diacrylate,pentaerythritol triacrylate, pentaerythritol tetraacrylate,dipentaerythritol diacrylate, dipentaerythritol triacrylate,dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate,dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate,pentaerythritol dimethacrylate, pentaerythritol trimethacrylate,dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate,tripentaerythritol octamethacrylate, pentaerythritol diitaconate,dipentaerythritol tris-itaconate, dipentaerythritol pentaitaconate,dipentaerythritol hexaitaconate, ethylene glycol diacrylate,1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanedioldiitaconate, sorbitol triacrylate, sorbitol tetraacrylate,pentaerythritol-modified triacrylate, sorbitol tetra methacrylate,sorbitol pentaacrylate, sorbitol hexaacrylate, oligoester acrylates andmethacrylates, glycerol diacrylate and triacrylate, 1,4-cyclohexanediacrylate, bisacrylates and bismethacrylates of polyethylene glycolwith a molecular weight of from 200 to 1500, or mixtures thereof.

Also suitable as components (a) are the amides of identical ordifferent, unsaturated carboxylic acids with aromatic, cycloaliphaticand aliphatic polyamines having preferably 2 to 6, especially 2 to 4,amino groups. Examples of such polyamines are ethylenediamine, 1,2- or1,3-propylenediamine, 1,2-, 1,3- or 1,4-butylenediamine,1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine,dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine,phenylenediamine, bisphenylenediamine, di-β-aminoethyl ether,diethylenetriamine, triethylenetetramine, di(β-aminoethoxy)- ordi(β-aminopropoxy)ethane. Other suitable polyamines are polymers andcopolymers, preferably with additional amino groups in the side chain,and oligoamides having amino end groups. Examples of such unsaturatedamides are methylenebisacrylamide, 1,6-hexamethylenebisacrylamide,diethylenetriaminetrismethacrylamide, bis(methacrylamidopropoxy)ethane,β-methacrylamidoethyl methacrylate andN[(β-hydroxyethoxy)-ethyl]acrylamide.

Suitable unsaturated polyesters and polyamides are derived, for example,from maleic acid and from diols or diamines. Some of the maleic acid canbe replaced by other dicarboxylic acids. They can be used together withethylenically unsaturated comonomers, for example styrene. Thepolyesters and polyamides may also be derived from dicarboxylic acidsand from ethylenically unsaturated diols or diamines, especially fromthose with relatively long chains of, for example 6 to 20 C atoms.Examples of polyurethanes are those composed of saturated or unsaturateddiisocyanates and of unsaturated or, respectively, saturated diols.

Polymers with (meth)acrylate groups in the side chain are likewiseknown. They may, for example, be reaction products of epoxy resins basedon novolaks with (meth)acrylic acid, or may be homo- or copolymers ofvinyl alcohol or hydroxyalkyl derivatives thereof which are esterifiedwith (meth)acrylic acid, or may be homo- and copolymers of(meth)acrylates which are esterified with hydroxyalkyl (meth)acrylates.

Other suitable polymers with acrylate or methacrylate groups in the sidechains are, for example, solvent soluble or alkaline soluble polyimideprecursors, for example poly(amic acid ester) compounds, having thephotopolymerizable side groups either attached to the backbone or to theester groups in the molecule, i.e. according to EP 624826. Sucholigomers or polymers can be formulated with the new photoinitiators andoptionally reactive diluents, like polyfunctional (meth)acrylates inorder to prepare highly sensitive polyimide precursor resists.

The photopolymerizable compounds can be used alone or in any desiredmixtures. It is preferred to use mixtures of polyol (meth)acrylates.

Examples of the component (a) are also polymers or oligomers having atleast two ethylenically unsaturated groups and at least one carboxylfunction within the molecule structure, such as a resin obtained by thereaction of a saturated or unsaturated polybasic acid anhydride with aproduct of the reaction of an epoxy compound and an unsaturatedmonocarboxylic acid, for example, photosensitive compounds as describedin JP 6-1638 and JP 10301276 and commercial products such as EB9696, UCBChemicals; KAYARAD TCR1025, Nippon Kayaku Co., LTD., or an additionproduct formed between a carboxyl group-containing resin and anunsaturated compound having an α,β-unsaturated double bond and an epoxygroup (for example, ACA200M, Deicel Industries, Ltd.).

As diluent, a mono- or multi-functional ethylenically unsaturatedcompound, or mixtures of several of said compounds, can be included inthe above composition up to 70% by weight based on the solid portion ofthe composition.

Subject of the invention also is a photopolymerizable composition asdescribed above, wherein the component (a) is a resin obtained by thereaction of a saturated or unsaturated polybasic acid anhydride with aproduct of the reaction of an epoxy resin and an unsaturatedmonocarboxylic acid.

Such components are for example described in JP06-1938, JP08-278629,JP08-278630, JP10-301276, JP2001-40022, JP10-221843, JP11-231523,JP2002-206014-A or JP2006-53569-A, the disclosure of which hereby isincorpoarted by reference.

The unsaturated compounds (a) can also be used as a mixture withnonphotopolymerizable, film-forming components. These may, for example,be physically drying polymers or solutions thereof in organic solvents,for instance nitrocellulose or cellulose acetobutyrate. They may also,however, be chemically and/or thermally curable (heat-curable) resins,examples being polyisocyanates, polyepoxides and melamine resins, aswell as polyimide precursors. The use of heat-curable resins at the sametime is important for use in systems known as hybrid systems, which in afirst stage are photopolymerized and in a second stage are crosslinkedby means of thermal aftertreatment.

The invention also provides compositions comprising as component (a) atleast one ethylenically unsaturated photopolymerizable compound which isemulsified or dissolved in water.

Many variants of such radiation-curable aqueous prepolymer dispersionsare commercially available. A prepolymer dispersion is understood asbeing a dispersion of water and at least one prepolymer dispersedtherein. The concentration of water in these systems is, for example,from 5 to 80% by weight, in particular from 30 to 60% by weight. Theconcentration of the radiation-curable prepolymer or prepolymer mixtureis, for example, from 95 to 20% by weight, in particular from 70 to 40%by weight. In these compositions the sum of the percentages given forwater and prepolymer is in each case 100, with auxiliaries and additivesbeing added in varying quantities depending on the intended use.

The radiation-curable, film-forming prepolymers which are dispersed inwater and are often also dissolved are aqueous prepolymer dispersions ofmono- or polyfunctional, ethylenically unsaturated prepolymers which areknown per se, can be initiated by free radicals and have for example acontent of from 0.01 to 1.0 mol of polymerizable double bonds per 100 gof prepolymer and an average molecular weight of, for example, at least400, in particular from 500 to 10′000. Prepolymers with higher molecularweights, however, may also be considered depending on the intendedapplication. Use is made, for example, of polyesters containingpolymerizable C—C double bonds and having an acid number of not morethan 10, of polyethers containing polymerizable C—C double bonds, ofhydroxyl-containing reaction products of a polyepoxide, containing atleast two epoxide groups per molecule, with at least oneα,β-ethylenically unsaturated carboxylic acid, of polyurethane(meth)acrylates and of acrylic copolymers which containα,β-ethylenically unsaturated acrylic radicals, as are described in EP12339. Mixtures of these prepolymers can likewise be used. Also suitableare the polymerizable prepolymers described in EP 33896, which arethioether adducts of polymerizable prepolymers having an averagemolecular weight of at least 600, a carboxyl group content of from 0.2to 15% and a content of from 0.01 to 0.8 mol of polymerizable C—C doublebonds per 100 g of prepolymer. Other suitable aqueous dispersions, basedon specific alkyl (meth)acrylate polymers, are described in EP 41125,and suitable waterdispersible, radiation-curable prepolymers of urethaneacrylates can be found in DE 2936039. Further additives which may beincluded in these radiation-curable aqueous prepolymer dispersions aredispersion auxiliaries, emulsifiers, antioxidants, e.g.2,2-thiobis(4-methyl-6t-butylphenol) or 2,6-di-t-butylphenol, lightstabilizers, dyes, pigments, fillers, such as glass or alumina, forexample talc, gypsum, silicic acid, rutile, carbon black, zinc oxide,iron oxides, reaction accelerators, levelling agents, lubricants,wetting agents, thickeners, flatting agents, antifoams and otherauxiliaries customary in paint technology. Suitable dispersionauxiliaries are water-soluble organic compounds which are of highmolecular mass and contain polar groups, examples being polyvinylalcohols, polyvinylpyrrolidone or cellulose ethers. Emulsifiers whichcan be used are nonionic emulsifiers and, if desired, ionic emulsifiersas well.

It is of course also possible to add other known photoinitiators (c),for example mixtures with camphor quinone; benzophenone, benzophenonederivatives, such as for example given below as sensitzers; ketalcompounds, as for example benzildimethylketal (Irgacure® 651);acetophenone, acetophenone derivatives, for example α-hydroxycycloalkylphenyl ketones or α-hydroxyalkyl phenyl ketones, such as for example2-hydroxy-2-methyl-1-phenyl-propanone (Darocur® 1173),1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure® 184),1-(4-dodecylbenzoyl)-1-hydroxy-1-methyl-ethane, 1-(4-isopropylbenzoyl)-1-hydroxy-1-methyl-ethane,1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one(Irgacure® 2959);2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one(Irgacure®127);2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-phenoxy]-phenyl}-2-methyl-propan-1-one;1-[4-(benzoyl-phenyl-thia)phenyl]-2-methyl-2-(p-tolylsulfonyl)-propane-1-one(Esacure® 1001M); oligomeric α-hydroxyalkyl phenyl ketones e.g.Esacure®ONE, Esacure®KIP 100; dialkoxyacetophenones,α-aminoacetophenones, e.g.(4-methylthiobenzoyl)-1-methyl-1-morpholinoethane (Irgacure® 907),(4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane (Irgacure® 369),(4-morpholinobenzoyl)-1-(4-methyl benzyl)-1-dimethylaminopropane(Irgacure® 379),(4-(2-hydroxyethyl)aminobenzoyl)-1-benzyl-1-dimethylaminopropane),(3,4-dimethoxybenzoyl)-1-benzyl-1-dimethylaminopropane;4-aroyl-1,3-dioxolanes, benzoin alkyl ethers, phenylglyoxalic esters andderivatives thereof, e.g. methyl α-oxo benzeneacetate, oxo-phenyl-aceticacid 2-(2-hydroxy-ethoxy)-ethyl ester, dimeric phenylglyoxalic esters,e.g. oxo-phenyl-acetic acid1-methyl-2-[2-(2-oxo-2-phenyl-acetoxy)-propoxy]-ethyl ester (Irgacure®754); other oximeesters, e.g. 1,2-octanedione1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime) (Irgacure® OXE01), ethanone1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime)(Irgacure® OXE02), 9H-thioxanthene-2-carboxaldehyde9-oxo-2-(O-acetyloxime), peresters, e,g. benzophenone tetracarboxylicperesters as described for example in EP 126541, monoacyl phosphineoxides, e.g. (2,4,6-trimethylbenzoyl)diphenylphosphine oxide(Darocur®TPO), ethyl (2,4,6 trimethylbenzoyl phenyl) phosphinic acid ester;bisacylphosphine oxides, e.g.bis(2,6-dimethoxy-benzoyl)-(2,4,4-trimethylpentyl)phosphine oxide,bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure® 819),bis(2,4,6-trimethylbenzoyl)-2,4-dipentoxyphenylphosphine oxide,trisacylphosphine oxides, halomethyltriazines, e.g.2-[2-(4-methoxy-phenyl)-vinyl]-4,6-bis-trichloromethyl-[1,3,5]triazine,2-(4-methoxy-phenyl)-4,6-bis-trichloromethyl-[1,3,5]-triazene,2-(3,4-dimethoxy-phenyl)-4,6-bis-trichloromethyl-[1,3,5]triazine,2-methyl-4,6-bis-trichloromethyl-[1,3,5]triazine,hexaarylbisimidazole/coinitiators systems, e.g.ortho-chlorohexaphenyl-bisimidazole combined with2-mercaptobenzthiazole, ferrocenium compounds, or titanocenes, e.g.bis(cyclopentadienyl)-bis(2,6-difluoro-3-pyrrylphenyl)titanium(Irgacure®784).

Further, borate compounds can be used as coinitiators. The Darocur® andIrgacure® compounds are available from BASF SE; Esacure is availablefrom Lamberti SPA. Where the novel photoinitiator systems are employedin hybrid systems, use is made, in addition to the novel free-radicalhardeners, of cationic photoinitiators, of peroxide compounds, such asbenzoyl peroxide (other suitable peroxides are described in U.S. Pat.No. 4,950,581 column 19, lines 17-25), of aromatic sulfonium-,phosphonium- or iodonium salts as described for example in U.S. Pat. No.4,950,581, column 18, line 60 to column 19, line 10 orcyclopentadienylarene-iron(II) complex salts, for example(η⁶-iso-propylbenzene)(η⁵-cyclopentadienyl)iron(II) hexafluorophosphate,as well as oxime sulfonic acid esters, as are, for example described inEP780729. Also pyridinium and (iso)quinolinium salts as described e.g.in EP497531 and EP441232 may be used in combination with the newphotoinitiators.

The new photoinitiators, either alone or in mixtures with other knownphotoinitiators and sensitizers, can be used also in the form of adispersion or emulsion in water or aqueous solutions. In case thecompounds are used in emulsions or dispersions conveniently customarydispersants or emulsifiers are added to prepare a stable emulsion ordispersion. Corresponding suitable additives are known to the personskilled in the art.

The photopolymerizable compositions generally comprise 0.05 to 25% byweight, preferably 0.01 to 10% by weight, in particular 0.01 to 5% byweight of the photoinitiator, based on the solid composition. The amountrefers to the sum of all photoinitiators added, if mixtures ofinitiators are employed. Accordingly, the amount either refers to thephotoinitiator (b) or the photoinitiators (b)+(c).

In addition to the photoinitiator the photopolymerizable mixtures mayinclude various additives (d). Examples of these are thermal inhibitors,which are intended to prevent premature polymerization, examples beinghydroquinone, hydroquinone derivatives, p-methoxyphenol, β-naphthol orsterically hindered phenols, such as 2,6-di-tert-butyl-p-cresol In orderto increase the stability on storage in the dark it is possible, forexample, to use copper compounds, such as copper naphthenate, stearateor octoate, phosphorus compounds, for example triphenylphosphine,tributylphosphine, triethyl phosphite, triphenyl phosphite or tribenzylphosphite, quaternary ammonium compounds, for exampletetramethylammonium chloride or trimethylbenzylammonium chloride, orhydroxylamine derivatives, for example N-diethylhydroxylamine. Toexclude atmospheric oxygen during the polymerization it is possible toadd paraffin or similar wax-like substances which, being of inadequatesolubility in the polymer, migrate to the surface in the beginning ofpolymerization and form a transparent surface layer which prevents theingress of air. It is also possible to apply an oxygen-impermeable layeron top of the coating, for example poly(vinylalcohol-co-vinylacetate).Light stabilizers which can be added in a small quantity are UVabsorbers, for example those of the hydroxyphenylbenzotriazole,hydroxyphenyl-benzophenone, oxalamide or hydroxyphenyl-s-triazine type.These compounds can be used individually or in mixtures, with or withoutsterically hindered amines (HALS). Examples of such UV absorbers andlight stabilisers are disclosed in WO 04/074328, page 12, line 9 to page14, line 23, said disclosure hereby is incorporated by reference.

To accelerate the photopolymerization it is possible to add amines ascomponent (d), for example triethanolamine, N-methyldiethanolamine,ethyl-p-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate,2-ethylhexyl-p-dimethylaminobenzoate,octyl-para-N,N-dimethylaminobenzoate,N-(2-hydroxyethyl)-N-methyl-para-toluidine or Michler's ketone. Theaction of the amines can be intensified by the addition of aromaticketones of the benzophenone type. Examples of amines which can be usedas oxygen scavengers are substituted N,N-dialkylanilines, as aredescribed in EP339841. Other accelerators, coinitiators and autoxidizersare thiols, thioethers, disulfides, phosphonium salts, phosphine oxidesor phosphines, as described, for example, in EP438123, in GB2180358 andin JP Kokai Hei 6-68309.

It is further possible to add chain transfer agents which are customaryin the art to the compositions according to the invention as component(d). Examples are mercaptans, amines and benzothiazol.

Photopolymerization can also be accelerated by adding furtherphotosensitizers or coinitiators (as component (d)) which shift orbroaden the spectral sensitivity. These are, in particular, aromaticcompounds, for example benzophenone and derivatives thereof,thioxanthone and derivatives thereof, anthraquinone and derivativesthereof, coumarin and phenothiazine and derivatives thereof, and also3-(aroylmethylene)thiazolines, rhodanine, camphorquinone, but alsoeosine, rhodamine, erythrosine, xanthene, thioxanthene, acridine, e.g.9-phenylacridine, 1,7-bis(9-acridinyl)heptane,1,5-bis(9-acridinyl)pentane, cyanine and merocyanine dyes. Examples ofsuitable sensitizer compounds (d) are disclosed in WO 06/008251, page36, line 30 to page 38, line 8, the disclosure of which is herebyincorporated by reference.

A photopolymerizable composition, comprising as further additive (d) aphotosensitizer compound selected from the group consisting ofbenzophenone and its derivatives, thioxanthone and its derivatives,anthraquinone and its derivatives, or coumarine and its derivatives ispreferred.

Examples of benzophenone derivatives, thioxanthone derivatives,anthraquinone deriatives and coumarin derivatives are benzophenone,4-phenyl benzophenone, 4-methoxy benzophenone, 4,4′-dimethoxybenzophenone, 4,4′-dimethyl benzophenone, 4,4′-dichlorobenzophenone4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone,4,4′-bis(methylethylamino)benzophenone,4,4′-bis(p-isopropylphenoxy)benzophenone, 4-methyl benzophenone,2,4,6-trimethylbenzophenone, 4-(4-methylthiophenyl)-benzophenone,3,3′-dimethyl-4-methoxy benzophenone, methyl-2-benzoylbenzoate,4-(2-hydroxyethylthio)-benzophenone, 4-(4-tolylthio)benzophenone,1-[4-(4-benzoyl-phenylsulfanyl)-phenyl]-2-methyl-2-(toluene-4-sulfonyl)-propan-1-one,4-benzoyl-N,N,N-trimethylbenzenemethanaminium chloride,2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-1-propanaminium chloridemonohydrate, 4-(13-acryloyl-1,4,7,10,13-pentaoxatridecyl)-benzophenone,4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyl)oxy]ethyl-benzenemethanaminiumchloride; thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone,1-chloro-4-propoxythioxanthone, 2-dodecylthioxanthone,2,4-diethylthioxanthone, 2,4-dimethylthioxanthone,1-methoxycarbonylthioxanthone, 2-ethoxycarbonylthioxanthone,3-(2-methoxyethoxycarbonyl)-thioxanthone, 4-butoxyarbnylthioxanthone,3-butoxycarbonyl-7-methylthioxanthone, 1-cyano-3chlorothioxanthone,1-ethoxycarbonyl-3-chlorothioxanthone,1-ethoxycarbonyl-3-ethoxythioxanthne,1-ethoxycarbonyl-3-aminothioxanthone,1-ethoxycarbonyl-3-phenylsulfurylthioxanthone,3,4-di-[2-(2-methoxyethoxyl)ethoxycarbonyl]-thioxanthone,1,3-dimethyl-2-hydroxy-9 Hthioxanthen-9-one 2-ethylhexylether,1-ethoxycarbonyl-3-(1-methyl-1-morpholinothyl)-thioxanthone,2-methyl-6-dimethoxymethyl-thioxanthone,2-methyl-6-(1,1-dimethxyenzyl)-thioxanthone,2-morpholinomethylthioxanthone, 2-methyl-6-morpholinoethylhioxanthone,N-allylthioxanthone-3,4-dicarboximide,N-octylthioxanthone-3,4-dicarbximide,N-(1,1,3,3-tetramethylbutyl)-thioxanthone-3,4-dicarboximide,1-phenoxythioanhone, 6-ethoxycarbonyl-2methoxythioxanthone,6-ethoxycarbonyl-2-methylthioxanhone, thioxanthone-2-carboxylic acidpolyethyleneglycol ester,2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthon-2-yloxy)-N,N,N-trimethyl-1-propanaminiumchloride, couarin 1, Coumarin 2, Coumarin 6, Coumarin 7, Coumarin 30,Coumarin 102, Coumarin 106, Coumarin 138, Coumarin 152, Coumarin 153,Coumarin 307, Coumarin 314, Coumarin 314T, Coumarin 334, Coumarin 337,Coumarin 500, 3-benzoyl coumarin, 3-benzoyl-7-methoxycoumarin,3-benzoyl-5,7-di methoxycoumarin, 3-benzoyl-5,7-dipropoxycoumarin,3-benzoyl-6,8-dichlorocoumarin, 3-benzoyl-6-chloro-coumarin,3,3′-carbonyl-bis[5,7-di(propoxy)coumarin],3,3′-carbonyl-bis(7-methoxycoumarin),3,3′-carbonyl-bis(7-diethylamino-coumarin), 3-isobutyroylcoumarin,3-benzoyl-5,7-dimethoxy-coumarin, 3-benzoyl-5,7-diethoxy-coumarin,3-benzoyl-5,7-dibutoxycoumarin,3-benzoyl-5,7-di(methoxyethoxy)-coumarin,3-benzoyl-5,7-di(allyloxy)coumarin, 3-benzoyl-7-dimethylaminocoumarin,3-benzoyl-7-diethylaminocoumarin, 3-isobutyroyl-7-dimethylaminocoumarin,5,7-dimethoxy-3-(1-naphthoyl)-coumarin,5,7-diethoxy-3-(1-naphthoyl)-coumarin, 3-benzoylbenzo[f]coumarin,7-diethylamino-3-thienoylcoumarin,3-(4-cyanobenzoyl)-5,7-dimethoxycoumarin,3-(4-cyanobenzoyl)-5,7-dipropoxycoumarin,7-dimethylamino-3-phenylcoumarin, 7-diethylamino-3-phenylcoumarin, thecoumarin derivatives disclosed in JP 09-179299-A and JP 09-325209-A, forexample7-[{4-chloro-6-(diethylamino)-S-triazine-2-yl}amino]-3-phenylcoumarin,9,10-anthraquinone and anthracene.

The curing process can be assisted by adding photosensitizers, inparticular, in compositions which are pigmented (for example withtitanium dioxide), and also by adding a component which under thermalconditions forms free radicals, for example an azo compound such as2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), a triazene, diazosulfide, pentazadiene or a peroxy compound, for instance a hydroperoxideor peroxy-carbonate, for example t-butyl hydroperoxide, as described forexample in EP245639. The compositions according to the invention maycomprise as further additive (d) a photoreducable dye, e.g., xanthene-,benzoxanthene-, benzothioxanthene, thiazine-, pyronine-, porphyrine- oracridine dyes, and/or trihalogenmethyl compounds which can be cleaved byirradiation. Similar compositions are for example described in EP445624.

Further additives known in the art may be added as component (d), as forexample flow improvers, adhesion promoters, such asvinyltrimethoxysilane, vinyltriethoxysilanevinyltris(2-methoxyethoxy)silane,N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,N-(2-aminoethyl)3-aminopropyltrimethoxysilane,3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane,3-glycidoxypropylmethyldimethoxysilane,2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane,3-methacryloxypropyltrimethoxysilane and3-mercaptopropyltrimethoxysilane. Surfactants, optical brighteners,pigments, dyes, wetting agents, levelling assistants, dispersants,aggregation preventers, antioxidants or fillers are further examples foradditives (d).

In order to cure thick and pigmented coatings it is appropriate to addglass microspheres or pulverized glass fibres, as described for examplein U.S. Pat. No. 5,013,768.

Further suitable components (d) are, as already mentioned above,surfactants and dispersants and other components, in particular tosupport the application of pigments or colorants in the formulation.

It is preferred to apply a surface treatment to the pigments in order tomake the pigment easy to disperse and to stabilize the resultant pigmentdispersion. The surface treatment reagents are, for example,surfactants, polymeric dispersants, general texture improving agents,pigment derivatives and mixtures thereof. It is especially preferredwhen the colorant composition according to the invention comprises atleast one polymeric dispersant and/or at least pigment derivative.

Suitable surfactants include anionic surfactants such as alkylbenzene-or alkylnahthalene-sulfonates, alkylsulfosuccinates or naphthaleneformaldehyde sulfonates; cationic surfactants including, for example,quaternary salts such as benzyl tributyl ammonium chloride; or nonionicor amphoteric surfactants such as polyoxyethylene surfactants and alkyl-or amidopropyl betaines, respectively.

Illustrative examples of the surfactant include polyoxyethylene alkylethers such as polyoxyethylene lauryl ether, polyoxyethylene stearylether and polyoxyethylene oleyl ether; polyoxyethylene alkylphenylethers such as polyoxyethylene octylphenyl ether and polyoxyethylenenonylphenyl ether; polyethylene glycol diesters such as polyethyleneglycol dilaurate and polyethylene glycol distearate; sorbitan fatty acidesters; fatty acid modified polyesters; tertiary amine modifiedpolyurethanes; polyethyleneimines; those available under the trade namesof KP (a product of Shin-Etsu Chemical Co., Ltd), Polyflow (a product ofKYOEISHA CHEMICAL Co., Ltd), F-Top (a product of Tochem Products Co.,Ltd), MEGAFAC (a product of Dainippon Ink & Chemicals, Inc.), Fluorad (aproduct of Sumitomo 3M Ltd), Asahi Guard and Surflon (products of AsahiGlass Co., Ltd); and the like.

These surfactants may be used alone or in admixture of two or more.

The surfactant is generally used in an amount of 50 parts or less byweight, preferably 0 to 30 parts by weight, based on 100 parts by weightof the colorant composition.

Polymeric dispersants include high molecular weight polymers withpigment affinic groups. Examples are: statistical co-polymers comprisedfrom, for instance, styrene derivatives, (meth)acrylates and(meth)acrylamides, and such statistical co-polymers modified by postmodification; block co-polymers and/or comb polymers comprised from, forinstance, styrene derivatives, (meth)acrylates and (meth)acrylamides,and such block co-polymers and/or comb polymers modified by postmodification; polyethylenimines, which for instance is crafted withpolyesters; polyamines, which for instance is crafted with polyesters;and many kinds of (modified) polyurethanes.

Polymeric dispersants may also be employed. Suitable polymericdispersants are, for example, BYK's DISPERBYK® 101, 115, 130, 140, 160,161, 162, 163, 164, 166, 168, 169, 170, 171, 180, 182, 2000, 2001, 2009,2020, 2025, 2050, 2070, 2090, 2091, 2095, 2096, 2150, 2163, 2164, BASFsEFKA® 4008, 4009, 4010, 4015, 4020, 4046, 4047, 4050, 4055, 4060, 4061,4080, 4300, 4310, 4320, 4330, 4340, 4400, 4401, 4402, 4403, 4406, 4500,4510, 4520, 4530, 4540, 4550, 4560, 4570, 4580, 4585, 4590, 4800,Ajinomoto Fine Techno's Ajisper PB®711, 821, 822, 823, 824, 827, 881,Lubrizol's SOLSPERSE® 1320, 13940, 17000, 20000, 21000, 24000, 26000,27000, 28000, 31845, 32000, 32500, 32550, 32600, 33500, 34750, 36000,36600, 37500, 38500, 39000, 41000, 41090, 44000, 53095, Kawaken FineChemicals' Hinoact KF-1300M, T-6000, T-8000, T-8000E, T-9050, KusumotoChemicals' Disparlon PW-36, DA-325, DA-375, DA-7301, KyoheishaChemical's Flowlen DOPA-15B, DOPA-15BHFS, DOPA-17HF, DOPA-22, DOPA-33,G-600, G-700, G-820, G-900, NC-500, KDG-2400 and combinations thereof.

It is preferred to use EFKA® 4046, 4047, 4060, 4061, 4300, 4310, 4320,4330, 4340, 4585, DISPERBYK® 161, 162, 163, 164, 165, 166, 168, 169,170, 2000, 2001, 2020, 2050, 2090, 2091, 2095, 2096, 2105, 2150, 2163,2164, PB®711, 821, 822, 823, 824, 827, 881, SOLSPERSE® 24000, 31845,32500, 32550, 32600, 33500, 34750, 36000, 36600, 37500, 39000, 41090,44000, 53095, Hinoact T-6000, T-8000E, Disparlon PW-36, DA-7301, andcombinations thereof as dispersant.

Suitable texture improving agents are, for example, fatty acids such asstearic acid or behenic acid, and fatty amines such as laurylamine andstearylamine. In addition, fatty alcohles or ethoxylated fatty alcohlespolyols such as aliphatic 1,2-diols or epoxidized soy bean oil, waxes,resin acids and resin acid salts may be used for this purpose.

Suitable pigment dispersants are, for example, copper phthalocyaninederivatives such as BASF's EFKA® 6745, Lubrizol's SOLSPERSE® 5000,12000, BYK's SYNERGIST 2100 and azo derivatives such as EFKA® 6750,SOLSPERSE® 22000 and SYNERGIST 2105.

The above mentioned dispersants and surfactants for pigments are forexample employed in compositions of the present invention which are usedas resist formulations, in particular in color filter formulations.

Subject of the invention also is a photopolymerizable composition asdescribed above as further additive (d) comprising a dispersant or amixture of dispersants as well as a photopolymerizable composition asdescribed above as further additive (d) comprising a pigment or amixture of pigments or a mixture of one or more pigments with one ormore dyes.

Suitable pigments and dyes, in particular for color filter applicationsare described below.

The choice of additive(s) (d) is made depending on the field ofapplication and on properties required for this field. The additivesdescribed above are customary in the art and accordingly are added inamounts which are usual in the respective application.

Binders (e) as well can be added to the novel compositions. This isparticularly expedient when the photopolymerizable compounds are liquidor viscous substances. The quantity of binder may, for example, be2-98%, preferably 5-95% and especially 20-90%, by weight relative to theoverall solids content. The choice of binder is made depending on thefield of application and on properties required for this field, such asthe capacity for development in aqueous and organic solvent systems,adhesion to substrates and sensitivity to oxygen.

Examples of suitable binders are polymers having a molecular weight ofabout 2′000 to 2′000′000, preferably 3′000 to 1′000′000. Examples ofalkali developable binders are acrylic polymer having carboxylic acidfunction as a pendant group, such as conventionally known copolymersobtained by copolymerizing an ethylenic unsaturated carboxylic acid suchas (meth)acrylic acid, 2-carboxyethyl (meth)acrylic acid,2-carboxypropyl (meth)acrylic acid itaconic acid, crotonic acid, maleicacid, fumaric acid and ω-carboxypolycaprolactone mono(meth)acrylate,with one or more monomers selected from esters of (meth)acrylic acid,such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl(meth)acrylate, butyl (meth)acrylate, benzyl (meth)acrylate,2-ethylhexyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl(meth)acrylate, glycerol mono(meth)acrylate,tricyclo[5.2.1.0^(2,6)]decan-8-yl (meth)acrylate, glycidyl(meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl(meth)acrylate, 6,7-epoxyheptyl (meth)acrylate; vinyl aromaticcompounds, such as styrene, α-methylstyrene, vinyltoluene,p-chlorostyrene, vinyl benzyl glycidyl ether; amide type unsaturatedcompounds, (meth)acrylamide diacetone acrylamide, N-methylolacrylamide,N-butoxymethacrylamide; and polyolefin type compounds, such asbutadiene, isoprene, chloroprene and the like; methacrylonitrile, methylisopropenyl ketone, mono-2-[(meth)acryloyloxy]ethyl succinate,N-phenylmaleimide, maleic anhydride, vinyl acetate, vinyl propionate,vinyl pivalate, polystyrene macromonomer, or polymethyl (meth)acrylatemacromonomer. Examples of copolymers are copolymers of acrylates andmethacrylates with acrylic acid or methacrylic acid and with styrene orsubstituted styrene, phenolic resins, for example novolak,(poly)hydroxystyrene, and copolymers of hydroxystyrene with alkylacrylates, acrylic acid and/or methacrylic acid. Preferable examples ofcopolymers are copolymers of methyl methacrylate/methacrylic acid,copolymers of benzyl methacrylate/methacrylic acid, copolymers of methylmethacrylate/ethyl acrylate/methacrylic acid, copolymers of benzylmethacrylate/methacrylic acid/styrene, copolymers of benzylmethacrylate/methacrylic acid/hydroxyethyl methacrylate, copolymers ofmethyl methacrylate/butyl methacrylate/methacrylic acid/styrene,copolymers of methyl methacrylate/benzyl methacrylate/methacrylicacid/hydroxyphenyl methacrylate. Examples of solvent developable binderpolymers are poly(alkyl methacrylates), poly(alkyl acrylates),poly(benzylmethacrylate-co-hydroxyethylmethacrylate-co-methacrylicacid), poly(benzylmethacrylate-co-methacrylic acid); cellulose estersand cellulose ethers, such as cellulose acetate, celluloseacetobutyrate, methylcellulose, ethylcellulose; polyvinylbutyral,polyvinylformal, cyclized rubber, polyethers such as polyethylene oxide,polypropylene oxide and polytetrahydrofuran; polystyrene, polycarbonate,polyurethane, chlorinated polyolefins, polyvinyl chloride, vinylchloride/vinylidene copolymers, copolymers of vinylidene chloride withacrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate,copoly(ethylene/vinyl acetate), polymers such as polycaprolactam andpoly(hexamethylene adipamide), and polyesters such as poly(ethyleneglycol terephtalate) and poly(hexamethylene glycol succinate) andpolyimide binder resins.

The polyimide binder resin in the present invention can either be asolvent soluble polyimide or a polyimide precursor, for example, apoly(amic acid).

Preferred is a photopolymerizable composition, comprising as binderpolymer (e), a copolymer of methacrylate and methacrylic acid.

Interesting further are polymeric binder components as described e.g. inJP 10-171119-A, in particular for use in color filters.

Subject of the invention further is a photopolymerizable composition asdescribed above, wherein the component (a) is a resin obtained by thereaction of a saturated or unsaturated polybasic acid anhydride with aproduct of the reaction of an epoxy resin and an unsaturatedmonocarboxylic acid.

The photopolymerizable compositions can be used for various purposes,for example as printing ink, e.g. screen printing inks, inks for offset-or flexo printing, as a clear finish, as a white or colored finish, forexample for wood or metal, as powder coating, as a coating material,inter alia for paper, wood, metal or plastic, as a daylight-curablecoating for the marking of buildings and roadmarking, for photographicreproduction techniques, for holographic recording materials, for imagerecording techniques or to produce printing plates which can bedeveloped with organic solvents or with aqueous alkalis, for producingmasks for screen printing, as dental filling compositions, as adhesives,as pressure-sensitive adhesives, as laminating resins, as etch resists,solder resists, electroplating resists, or permanent resists, bothliquid and dry films, as photostructurable dielectric, for printedcircuit boards and electronic circuits, as resists to manufacture colorfilters for a variety of display applications or to generate structuresin the manufacturing process of plasma-display panels andelectroluminescence displays, (as for example described in U.S. Pat. No.5,853,446, EP863534, JP 09-244230-A, JP10-62980-A, JP08-171863-A, U.S.Pat. No. 5,840,465, EP855731, JP05-271576-A, JP 05-67405-A) for theproduction of holographic data storage (HDS) material, for theproduction of optical switches, optical lattices (interference lattice),light circuits, for producing three-dimensional articles by mass curing(UV curing in transparent moulds) or by the stereolithography technique,as is described, for example, in U.S. Pat. No. 4,575,330, to producecomposite materials (for example styrenic polyesters, which may, ifdesired, contain glass fibres and/or other fibres and other auxiliaries)and other thick-layered compositions, for coating or sealing electroniccomponents and integrated circuits, or as coatings for optical fibres,or for producing optical lenses, e.g. contact lenses or Fresnel lenses.The compositions according to the invention are further suitable for theproduction of medical equipment, auxiliaries or implants. Further, thecompositions according to the invention are suitable for the preparationof gels with thermotropic properties, as for example described inDE19700064 and EP678534.

The novel photoinitiators may additionally be employed as initiators foremulsion polymerizations, pearl polymerizations or suspensionpolymerizations, as polymerizetion initiators for fixing ordered statesof liquid-crystalline monomers and oligomers, or as initiators forfixing dyes on organic materials.

In coating materials, use is frequently made of mixtures of a prepolymerwith polyunsaturated monomers, which may additionally include amonounsaturated monomer as well. It is the prepolymer here whichprimarily dictates the properties of the coating film, and by varying itthe skilled worker is able to influence the properties of the curedfilm. The polyunsaturated monomer functions as a crosslinking agentwhich renders the film insoluble. The monounsaturated monomer functionsas a reactive diluent, which is used to reduce the viscosity without theneed to employ a solvent.

Unsaturated polyester resins are usually used in two-component systemstogether with a monounsaturated monomer, preferably with styrene. Forphotoresists, specific one-component systems are often used, for examplepolymaleimides, polychalcones or polyimides, as described in DE 2308830.

The novel photoinitiators can also be used for the polymerization ofradiation-curable powder coatings. The powder coatings can be based onsolid resins and monomers containing reactive double bonds, for examplemaleates, vinyl ethers, acrylates, acrylamides and mixtures thereof. Afree-radically UV-curable powder coating can be formulated by mixingunsaturated polyester resins with solid acrylamides (for example methylmethylacrylamidoglycolate) and a novel free-radical photoinitiator, suchformulations being as described, for example, in the paper “RadiationCuring of Powder Coating”, Conference Proceedings, Radtech Europe 1993by M. Wittig and Th. Gohmann. The powder coatings can also containbinders, as are described, for example, in DE 4228514 and in EP 636669.Free-radically UV-curable powder coatings can also be formulated bymixing unsaturated polyester resins with solid acrylates, methacrylatesor vinyl ethers and with a novel photoinitiator (or photoinitiatormixture). The powder coatings may also comprise binders as aredescribed, for example, in DE 4228514 and in EP 636669. The UV-curablepowder coatings may additionally comprise white or coloured pigments.For example, preferably rutiletitanium dioxide can be employed inconcentrations of up to 50% by weight in order to give a cured powdercoating of good hiding power. The procedure normally compriseselectrostatic or tribostatic spraying of the powder onto the substrate,for example metal or wood, melting of the powder by heating, and, aftera smooth film has formed, radiation-curing of the coating withultraviolet and/or visible light, using for example medium-pressuremercury lamps, metal halide lamps or xenon lamps. A particular advantageof the radiation-curable powder coatings over their heat-curablecounterparts is that the flow time after melting the powder particlescan be delayed in order to ensure the formation of a smooth, high-glosscoating. In contrast to heat-curable systems, radiation-curable powdercoatings can be formulated to melt at lower temperatures without theunwanted effect of shortening their lifetime. For this reason, they arealso suitable as coatings for heat-sensitive substrates, for examplewood or plastics. In addition to the novel photoinitiator systems, thepowder coating formulations may also include UV absorbers. Appropriateexamples are listed above in sections 1.-8.

The novel photocurable compositions are suitable, for example, ascoating materials for substrates of all kinds, for example wood,textiles, paper, ceramics, glass, plastics such as polyesters,polyethylene terephthalate, polyolefins or cellulose acetate, especiallyin the form of films, and also metals such as Al, Cu, Ni, Fe, Zn, Mg orCo and GaAs, Si or SiO₂ to which it is intended to apply a protectivelayer or, by means of imagewise exposure, to generate an image.

The novel radiation-sensitive compositions further find application asnegative resists, having a very high sensitivity to light and being ableto be developed in an aqueous alkaline medium without swelling. They aresuitable for the production of printing forms for relief printing,planographic printing, photogravure or of screen printing forms, for theproduction of relief copies, for example for the production of texts inbraille, for the production of stamps, for use in chemical milling or asa microresist in the production of integrated circuits. The compositionsfurther may be used as photopatternable dielectric layer or coating,encapsulating material and isolating coating in the production ofcomputer chips, printed boards and other electric or electroniccomponents. The possible layer supports, and the processing conditionsof the coating substrates, are just as varied.

The novel composition also relates to a photosensitive thermosettingresin composition and a method of forming a solder resist pattern by theuse thereof, and more particularly relates to a novel photosensitivethermosetting resin composition useful as materials for the productionof printed circuit boards, the precision fabrication of metallicarticles, the etching of glass and stone articles, the relief of plasticarticles, and the preparation of printing plates and particularly usefulas a solder resist for printed circuit boards and to a method of forminga solder resist pattern by the steps of exposing a layer of the resincomposition selectively to an actinic ray through a photomask having apattern and developing the unexposed part of the layer.

The solder resist is a substance which is used during the soldering of agiven part to a printed circuit board for the purpose of preventingmolten solder from adhering to irrelevent portions and protectingcircuits. It is, therefore, required to possess such properties as highadhesion, insulation resistance, resistance to soldering temperature,resistance to solvents, resistance to alkalis, resistance to acids, andresistance to plating.

Because the photocurable compositions according to the invention have agood thermal stability and are sufficiently resistant to inhibition byoxygen, they are particularly suitable for the production of colorfilters or color mosaic systems, such as described, for example, in EP320 264. Color filters usually are employed in the manufacturing of flatpanel displays such as LCD's, PDP(plasma panel display), EL(electroluminessence) display, and projection systems, image sensors,CCD (charge coupled device), and CMOS (complementary metal oxidesemiconductor) sensors for scanner, digital camera and video camera.

The color filters usually are prepared by forming red, green and bluepixels and a black matrix on a glass substrate. In these processesphotocurable compositions according to the invention can be employed. Aparticularly preferred method of use comprises adding of the coloringmatters, dyes and pigments of red, green and blue colors to thelight-sensitive resin composition of the present invention, coating ofthe substrate with the composition, drying of the coating with a shortheat treatment, patternwise exposure of the coating to actinic radiationand subsequent development of the pattern in an aqueous alkalinedeveloper solution and optionally a heat treatment. Thus, bysubsequently applying a red, green and blue pigmented coating, in anydesired order, on top of each other with this process a color filterlayer with red, green and blue color pixels can be produced.

The development is carried out by washing out the areas which were notpolymerized with a suitable alkali developing solution. This process isrepeated to form the image having plural colors.

In the light-sensitive resin composition of the present invention, witha process in which at least one or more picture elements are formed on atransparent substrate and then an exposure is given from a side of thetransparent substrate, on which the above picture elements are notformed, the above picture elements can be utilized as a light-shieldingmask. In this case, for example, in the case where an overall exposureis given, a position adjustment of a mask gets unnecessary and a concernon a position slippage thereof is removed. And, it is possible to cureall of the part on which the above picture elements are not formed.Further, in this case, it is possible as well to develop and remove apart of the portion on which the above picture elements are not formedby using partially a light-shielding mask.

Since in either case, no gap is formed between the picture elementswhich are formed formerly and those which are formed later, thecomposition of the present invention is suitable for, for example, aforming material for a color filter. To be concrete, the coloringmatters, dyes and pigments of red, green and blue colors are added tothe light-sensitive resin composition of the present invention, and theprocesses for forming an image are repeated to form the picture elementsof red, green and blue colors. Then, the light-sensitive resincomposition to which, for example, the black coloring materials, dyesand pigments are added is provided on an overall face. An overallexposure (or a partial exposure via a light-shielding mask) can beprovided thereon to form the picture elements of a black color all overthe spaces (or all but a partial region of the light-shielding mask)between the picture elements of red, green and blue colors.

In addition to a process in which the light-sensitive resin compositionis coated on a substrate and dried, the light-sensitive resincomposition of the present invention can be used as well for a layertransfer material. That is, the light-sensitive resin composition islayer-wise provided directly on a temporary support, preferably on apolyethylene terephthalate film, or on a polyethylene terephthalate filmon which an oxygen-shielding layer and a peeling layer or the peelinglayer and the oxygen-shielding layer are provided. Usually, a removablecover sheet made of a synthetic resin is laminated thereon for aprotection in handling. Further, there can be applied as well a layerstructure in which an alkali soluble thermoplastic resin layer and anintermediate layer are provided on a temporary support and further alight-sensitive resin composition layer is provided thereon (JP5-173320-A).

The above cover sheet is removed in use and the light-sensitive resincomposition layer is laminated on a permanent support. Subsequently,peeling is carried out between those layer and a temporary support whenan oxygen-shielding layer and a peeling layer are provided, between thepeeling layer and the oxygen-shielding layer when the peeling layer andthe oxygen-shielding layer are provided, and between the temporarysupport and the light-sensitive resin composition layer when either thepeeling layer or the oxygen-shielding layer is not provided, and thetemporary support is removed.

A metal support, glass, ceramics, and a synthetic resin film can be usedas a support for a color filter. Glass and a synthetic resin film whichis transparent and have an excellent dimension stability is particularlypreferred.

The thickness of the light-sensitive resin composition layer is usually0.1 to 50 micrometers, in particular 0.5 to 5 micrometers.

A diluted aqueous solution of an alkaline substance can be used as adeveloping solution for the light-sensitive resin composition of thepresent invention if the composition contains alkali soluble resin oralkali soluble monomers or oligomers, and further a developer solutionprepared by adding a small amount of a water-miscible organic solventthereto is included as well.

Examples of suitable alkaline materials include alkali metal hydroxides(for example, sodium hydroxide and potassium hydroxide), alkali metalcarbonates (for example, sodium carbonate and potassium carbonate),alkali metal bicarbonates (for example, sodium bicarbonate and potassiumbicarbonate), alkali metal silicates (for example, sodium silicate andpotassium silicate), alkali metal metasilicates (for example, sodiummetasilicate and potassium metasilicate), triethanolamine,diethanolamine, monoethanolamine, morpholine, tetraalkylammoniumhydroxides (for example, tetramethylammonium hydroxide), or trisodiumphosphate. The concetration of the alkaline substance is 0.01 to 30weight %, and pH is preferably 8 to 14.

Suitable organic solvents which are miscible with water includemethanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol,ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,ethylene glycol mono-n-butyl ether, diethyleneglycol dimethyl ether,propyleneglycol monomethyl ether acetate, ethyl-3-ethoxypropionate,methyl-3-methoxypropionate, n-butyl acetate, benzyl alcohol, acetone,methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone,2-pentanone, epsilon-caprolactone, gamma-butylolactone,dimethylformamide, dimethylacetoamide, hexamethylphosphoramide, ethyllactate, methyl lactate, epsilon-caprolactam, andN-methyl-pyrrolidinone. The concentration of the organic solvent whichis miscible with water is 0.1 to 30 weight %.

Further, a surface active agent can be added. The concentration of thesurface active agent is preferably 0.001 to 10 weight %. Such additivesare known in the art.

The light sensitive resin composition of the present invention can alsobe developed with organic solvents, including blends of two or moresolvents, not containing alkaline compounds. Suitable solvents includemethanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol,ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,ethylene glycol mono-n-butyl ether, diethyleneglycol dimethyl ether,propyleneglycol monomethyl ether acetate, ethyl-3-ethoxypropionate,methyl-3-methoxypropionate, n-butyl acetate, benzyl alcohol, acetone,methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone,2-pentanone, epsilon-caprolactone, gamma-butylolactone,dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyllactate, methyl lactate, epsilon-caprolactam, and N-methylpyrrolidinone.Optionally, water can be added to these solvents up to a level at whichstill a clear solution is obtained and at which sufficient solubility ofthe unexposed areas of the light sensitive composition is maintained.

The developer solution can be used in all forms known to the personskilled in the art, for example in form of a bath solution, puddle, or aspraying solution. In order to remove the non-cured portion of thelight-sensitive resin composition layer, there can be combined themethods such as rubbing with a rotary brush and rubbing with a wetsponge. Usually, the temperature of the developing solution ispreferably at and around room temperature to 40° C. The developing timeis changeable according to the specific kind of the light-sensitiveresin composition, the alkalinity and temperature of the developingsolution, and the kind and concentration of the organic solvent in thecase where it is added. Usually, it is 10 seconds to 2 minutes. It ispossible to put a rinsing step after the development processing.

A final heat treatment is preferably carried out after the developmentprocessing. Accordingly, a support having a layer which isphotopolymerized by exposing (hereinafter referred to as a photocuredlayer) is heated in an electric furnace and a drier, or the photocuredlayer is irradiated with an infrared lamp or heated on a hot plate. Theheating temperature and time depend on the composition used and thethickness of the formed layer. In general, heating is preferably appliedat about 120° C. to about 250° C., for about 5 to about 60 minutes.

The pigment which can be comprised in the composition according to thepresent invention, including a pigmented color filter resistcomposition, is preferably a processed pigment, for example a powdery orpasty product prepared by finely dispersing a pigment into at least oneresin selected from the group consisting of acrylic resin, vinylchloride-vinyl acetate copolymer, maleic acid resin and ethyl celluloseresin.

The red pigment comprises, for example, an anthraquinone type pigmentalone, a diketopyrolopyrole type pigment alone, a mixture of them or amixture consisting of at least one of them and a disazo type yellowpigment or an isoindoline type yellow pigment, in particular C. I.Pigment Red 177 alone, C. I. Pigment Red 254 alone, a mixture of C. I.Pigment Red 177 and C. I. Pigment Red 254 or a mixture consisting of atleast one member of C. I. Pigment Red 177 and C. I. Pigment Red 254, andC. I. Pigment Yellow 83 or C. I. Pigment Yellow 139 (“C.I.” refers tothe Color Index, known to the person skilled in the art and publiclyavailable).

Further suitable examples for the pigment are C.I. Pigment Red 9, 97,105, 122, 123, 144, 149, 168, 176, 179, 180, 185, 202, 207, 209, 214,222, 242, 244, 255, 264, 272 and C.I. Pigment Yellow 12, 13, 14, 17, 20,24, 31, 53, 55, 93, 95, 109, 110, 128, 129, 138, 139, 150, 153, 154,155, 166, 168, 185, 199, 213 and C.I. Pigment Orange 43.

Examples of the dyes for red color are C. I. Solvent Red 25, 27, 30, 35,49, 83, 89, 100, 122, 138, 149, 150, 160, 179, 218, 230, C. I. DirectRed 20, 37, 39, 44, and C. I. Acid Red 6, 8, 9, 13, 14, 18, 26, 27, 51,52, 87, 88, 89, 92, 94, 97, 111, 114, 115, 134, 145, 151, 154, 180, 183,184, 186, 198, C. I. Basic Red 12, 13, C. I. Disperse Red 5, 7, 13, 17and 58. The Red dyes can be used in combination with yellow and/ororange dyes. The green pigment comprises for instance a halogenatedphthalocyanine type pigment alone or its mixture with a disazo typeyellow pigment, an quinophthalone type yellow pigment or a metalcomplex, in particular C. I. Pigment Green 7 alone, C. I. Pigment Green36 alone, or a mixture consisting of at least one member of C. I.Pigment Green 7, C. I. Pigment Green 36 and C. I. Pigment Yellow 83, C.I. Pigment Yellow 138 or C. I. Pigment Yellow 150. Other suitable greenpigments are C.I. Pigment Green 15, 25 and 37.

Examples for suitable green dyes are C. I. Acid Green 3, 9, 16, C. I.Basic Green 1 and 4.

Examples for suitable blue pigments are phthalocyanine type pigments,used either alone or in combination with an dioxazine type violetpigment, for instance, C. I. Pigment Blue 15:6 alone, a combination ofC. I. Pigment Blue 15:6 and C. I. Pigment Violet 23. Further examplesfor blue pigments are such of C. I. Pigment Blue 15:3, 15:4, 16, 22, 28and 60. Other suitable pigments are C. I. Pigment Violet 14, 19, 23, 29,32, 37, 177 and C. I. Orange 73.

Examples for suitable blue dyes are C. I. Solvent Blue 25, 49, 68, 78,94, C. I. Direct Blue 25, 86, 90, 108, C. I. Acid Blue 1, 7, 9, 15, 103,104, 158, 161, C. I. Basic Blue 1, 3, 9, 25, and C. I. Disperse Blue198.

The pigment of the photopolymeric composition for black matrixpreferably comprises at least one member selected from the groupconsisting of carbon black, titanium black and iron oxide. However, amixture of other pigments which, in total, give the black appearance,can also be used. For example, also C. I. Pigment Black 1, 7 and 31 canbe used alone or in combination.

Other examples of the dyes used for color filter are C. I. SolventYellow 2, 5, 14, 15, 16, 19, 21, 33, 56, 62, 77, 83, 93, 162, 104, 105,114, 129, 130, 162, C. I. Disperse Yellow 3, 4, 7, 31, 54, 61, 201, C.I. Direct Yellow 1, 11, 12, 28, C. I. Acid Yellow 1, 3, 11, 17, 23, 38,40, 42, 76, 98, C. I. Basic Yellow 1, C. I. Solvent Violet 13, 33, 45,46, C. I. Disperse Violet 22, 24, 26, 28, C. I. Acid Violet 49, C. I.Basic Violet 2, 7, 10, C. I. Solvent Orange 1, 2, 5, 6, 37, 45, 62, 99,C. I. Acid Orange 1, 7, 8, 10, 20, 24, 28, 33, 56, 74, C. I. DirectOrange 1, C. I. Disperse Orange 5, C. I. Direct Brown 6, 58, 95, 101,173, C. I. Acid Brown 14, C. I. Solvent Black 3, 5, 7, 27, 28, 29, 35,45 and 46.

In some special cases of manufacturing color filters, complementarycolors, yellow, magenta, cyan and optionally green, are used instead ofred, green and blue. As yellow for this type of color filters, theabovementioned yellow pigments and dyes can be employed. Examples of thecolorants suitable for magenta color are C. I. Pigment Red 122, 144,146, 169, 177, C. I. Pigment Violet 19 and 23. Examples of cyan colorare aluminum phthalocyanine pigments, titanium phthalocyanine pigments,cobalt phthalocyanine pigments, and tin phthalocyanine pigments.

For any color, combinations of more than two pigments can also be used.Especially suitable in color filter applications are powdery processedpigments prepared by finely dispersing the above mentioned pigments intoa resin.

The concentration of the pigment in the total solid component (pigmentsof various colors and resin) is for example in the range of 5% to 80% byweight, in particular in the range of 20% to 45% by weight.

The pigments in the color filter resist composition have preferably amean particle diameter smaller than the wavelength of visible light (400nm to 700 nm). Particularly preferred is a mean pigment diameter of <100nm.

If necessary, the pigments may be stabilized in the photosensitivecomposition by pretreatment of the pigments with a dispersant to improvethe dispersion stability of the pigment in the liquid formulation.Suitable additives are described above.

Preferably, the color filter resist composition according to the presentinvention contains additionally at least one addition polymerizablemonomeric compound as component (a).

The ethylenically unsaturated compounds (a), also for the color filterresist applications are as described above

Suitable examples of esters as component (a) based on polyols aretrimethylolpropane tri(meth)acrylate, trimethylolpropanetri(acryloyloxypropyl)ether, trimethylolethane tri(meth)acrylate,ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate,triethylene glycol di(meth)acrylate, tetraethylene glycoldi(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentylglycol di(meth)acrylate, pentaerythritol di(meth)acrylate,pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate,pentaerythritol tri(meth)acrylate monooxalate, dipentaerythritoldi(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritoltetra(meth)acrylate, dipentaerythritol penta(meth)acrylate,dipentaerythritol hexa(meth)acrylate, dipentaerythritolpenta(meth)acrylate mono(2-hydroxyethyl) ether, tripentaerythritolocta(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanedioldiitaconate, hexanediol di(meth)acrylate, 1,4-cyclohexanedioldi(meth)acrylate, sorbitol tri(meth)acrylate, sorbitoltetra(meth)acrylate, sorbitol penta(meth)acrylate, sorbitolhexa(meth)acrylate, oligoester (meth)acrylates, glyceroldi(meth)acrylate and tri(meth)acrylate, di(meth)acrylates ofpolyethylene glycol with a molecular weight of from 200 to 1500,pentaerythritol diitaconate, dipentaerythritol trisitaconate,dipentaerythritol pentaitaconate, dipentaerythritol hexaitaconate,ethylene glycol diitaconate, propylene glycol diitaconate,1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethyleneglycol diitaconate, sorbitol tetraitaconate, ethylene glycoldicrotonate, tetramethylene glycol dicrotonate, pentaerythritoldicrotonate, ethylene glycol dimaleate, diethylene glycol dimaleate,triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitoltetramaleate, or mixtures thereof.

Other examples are pentaerythritol and dipentaerythritol derivativesshown in the following formula (XII) and (XIII):

wherein

M₁₀ is —(CH₂CH₂O)— or —[CH₂CH(CH₃)O]—, R₁₀₀ is —COCH═CH₂ or—COC(CH₃)═CH₂,

p is 0 to 6 (total of p: 3-24), and q is 0 to 6 (total of q: 2-16).

Examples of polyepoxides are those based on the abovementioned polyolsand epichlorohydrin. Typical examples arebis(4-glycidyloxyphenyl)methane, 2,2-bis(4-glycidyloxyphenyl)propane,2,2-bis(4-glycidyloxyphenyl)hexafluoropropane,9,9-bis(4-glycidyloxyphenyl)fluorene,bis[4-(2-glycidyloxyethoxy)phenyl]methane,2,2-bis[4-(2-glycidyloxyethoxy)phenyl]propane,2,2-bis[4-(2-glycidyloxyethoxy)phenyl]hexafluoropropane,9,9-bis[4-(2-glycidyloxyethoxy)phenyl]fluorene,bis[4-(2-glycidyloxypropoxy)phenyl]methane,2,2-bis[4-(2-glycidyloxypropoxy)phenyl]propane,2,2-bis[4-(2-glycidyloxypropoxy)phenyl]hexafluoropropane,9,9-bis[4-(2-glycidyloxypropoxy)phenyl]fluorene, and glycidyl ethers ofphenol and cresol novolacs.

Typical examples of component (a) based on polyepoxides are2,2-bis[4-{(2-hydroxy-3-acryloxy)propoxy}phenyl]propane,2,2-bis[4-{(2-hydroxy-3-acryloxy)propoxyethoxy}phenyl]propane,9,9-bis[4-{(2-hydroxy-3-acryloxy)propoxy}phenyl]fluorene,9,9-bis[4-{(2-hydroxy-3-acryloxy)propoxyethoxy}phenyl]fluorine, andreaction products of epoxy resins based on novolacs with (meth)acrylicacid.

Polyethers obtained from the reaction of the abovementioned polyols orpolyepoxides with the unsaturated counpounds with a hydroxy group suchas 2-hydroxyethyl (meth)acrylate, vinyl alcohol can also be used ascomponent (a).

Other examples for suitable compoents (a) are unsaturated urethanesderived from a polyisocyanate and an unsaturated compound having ahydroxy group or from a polyisocyanate, a polyol and an unsaturatedcompound having a hydroxy group.

Other examples are polyesters, polyamides, or polyurethanes havingethylenically unsaturated groups in the chain. Suitable unsaturatedpolyesters and polyamides are also derived, for example, from maleicacid and diols or diamines. Some of the maleic acid can be replaced byother dicarboxylic acids. The polyesters and polyamides may also bederived from dicarboxylic acids and ethylenically unsaturated diols ordiamines, especially from those with relatively long chains of, forexample 6 to 20 C atoms. Examples of polyurethanes are those composed ofsaturated or unsaturated diisocyanates and of unsaturated or,respectively, saturated diols.

Other suitable polymers with acrylate or methacrylate groups in the sidechains are, for example, solvent soluble or alkaline soluble polyimideprecursors, for example poly(amic acid ester) compounds, having thephotopolymerizable side groups either attached to the backbone or to theester groups in the molecule, i.e. according to EP 624826. Sucholigomers or polymers can be formulated optionally with reactivediluents, like polyfunctional (meth)acrylates in order to prepare highlysensitive polyimide precursor resists.

Further examples of the component (a) are also polymers or oligomershaving at least one carboxyl function and at least two ethylenicallyunsaturated groups within the molecular structure, such as a resinobtained by the reaction of a saturated or unsaturated polybasic acidanhydride with a product of the reaction of phenol or cresol novolacepoxy resin and an unsaturated monocarboxylic acid, for example,commercial products such as EB9696, UCB Chemicals; KAYARAD TCR1025,Nippon Kayaku Co., LTD. Examples of the polybasic acid anhydride aremaleic anhydride, succinic anhydride, itaconic anhydride, phthalicanhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,methyltetrahydrophathalic anhydride, glutaric anhydride, glutaconicanhydride, citraconic anhydride, diglycolic anhydride, iminodiaceticanhydride, 1,1-cyclopentanediacetic anhydride, 3,3-dimethylglutaricanhydride, 3-ethyl-3-methylglutaric anhydride, 2-phenylglutaricanhydride, homophthalic anhydride, trimellitic anhydride, chlorendicanhydride, pyromellitic dianhydride, benzophenone tetracarboxylic aciddianhydride, biphenyl tetracarboxylic acid dianhydride, andbiphenylether tetracarboxylic acid dianhydride.

Other examples are the products from the polycondensation reactionand/or addition reaction of the compound of formula (XIV) with one ormore abovementioned polybasic acid anhydrides.

wherein Y₁₀ is

R₂₀₀ is hydrogen or methyl,R₃₀₀ and R₄₀₀ independently of each other are hydrogen, methyl, Cl, orBr, M₂₀ is substituted or unsubstituted alkylene having 1 to 10 carbonatoms, x is 0 to 5, and y is 1 to 10. Examples of such compounds ascomponent (a) are described in JP2002-206014A, JP2004-69754A,JP2004-302245A, JP2005-77451 A, JP2005-316449A, JP2005-338328A andJP3754065B2.

Polymers or oligomers as abovementioned have for example a molecularweight of about 1′000 to 1′000′000, preferably 2′000 to 200′000 and anacid value of about 10 to 200 mg KOH/g, preferably 20 to 180 mg KOH/g.

A preferred photopolymerizable composition comprises as component (a) acompound having at least two ethylenically unsaturated bonds and atleast one carboxylic acid group in the molecule, in particular areaction product obtained by adding an epoxy group containingunsaturated compound to a part of the carboxyl groups of a carboxylicacid group containing polymer or a reaction product of the compoundshown below with one or more polybasic acid anhydrides. Furtherpreferred components (a) comprise a compound obtained from the reactionof a compound of the formula XIV with one or more polybasic acidanhydrides.

Further examples are reaction products obtained by adding an epoxy groupcontaining unsaturated compound to a part of the carboxyl groups of acarboxylic acid group containing polymer. As the carboxylic acidcontaining polymer, the abovementioned binder polymers which areresulting from the reaction of an unsaturated carboxylic acid compoundwith one or more polymerizable compounds, for example, copolymers of(meth)acrylic acid, benzyl (meth)acrylate, styrene and 2-hydroxyethyl(meth)acrylate, copolymers of (meth)acrylic acid, styrene andα-methystyrene, copolymers of (meth)acrylic acid, N-phenylmaleimide,styrene and benzyl (meth)acrylate, copolymers of (meth)acrylic acid andstyrene, copolymers of (meth)acrylic acid and benzyl (meth)acrylate,copolymers of tetrahydrofurfuryl (meth)acrylate, styrene and(meth)acrylic acid, and the like.

Examples of the unsaturated compounds having an epoxy group are givenbelow in the formula (V-1) (V-15);

wherein R₅₀ is hydrogen or methyl group, M₃₀ is substituted orunsubstituted alkylene having 1 to 10 carbon atoms.

Among these compounds, compounds having alicyclic epoxy groups areparticularly preferred, because these compounds have a high reactivitywith carboxyl group-containing resins, accordingly the reaction time canbe shortened. These compounds further do not cause gelation in theprocess of reaction and make it possible to carry out the reactionstably. On the other hand, glycidyl acrylate and glycidyl methacrylateare advantageous from the viewpoint of sensitivity and heat resistancebecause they have a low molecular weight and can give a high conversionof esterification.

Concrete examples of the abovementioned compounds are, for example areaction product of a copolymer of styrene, α-methyl styrene and acrylicacid or a copolymer of methyl methacrylate and acrylic acid with3,4-epoxycyclohexylmethyl (meth)acrylate.

Unsaturated compounds having a hydroxy group such as 2-hydroxyethyl(meth)acrylate and glycerol mono(meth)acrylate can be used instead ofthe above mentioned epoxy group containing unsaturated compounds as thereactant for carboxylic acid group containing polymers.

Other examples are half esters of anhydride containing polymers, forexample reaction products of a copolymer of maleic anhydride and one ormore other polymerizable compounds with (meth)acrylates having analcoholic hydroxy group such as 2-hydroxyethyl (meth)acrylate or havingan epoxy group for example such as the compounds described in theformula (V-1) (V-15).

Reaction products of polymers having alcoholic hydroxy groups such ascopolymers of 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid, benzymethacylate and styrene, with (meth)acrylic acid or (meth)acryl chloridecan also be used as component (a).

Other examples are reaction products of a polyester with terminalunsaturated groups, which is obtained from the reaction of a dibasicacid anhydride and a compound having at least two epoxy groups followedby further reaction with an unsaturated compound, with a polybasic acidanhydride.

Further examples are resins obtained by the reaction of a saturated orunsaturated polybasic acid anhydride with a reaction product obtained byadding epoxy group containing (meth)acrylic compound to all of thecarboxyl groups of a carboxylic acid containing polymer as mentionedabove.

The photopolymerizable compounds can be used alone or in any desiredmixtures.

In a color filter resist composition the whole amount of the monomerscontained in the photopolymerizable composition is preferably 5 to 80%by weight, in particular 10 to 70% by weight based on the whole solidcontents of the composition, i.e. the amount of all components withoutthe solvent(s).

As the binder used in the color filter resist composition, which issoluble in an alkaline aqueous solution and insoluble in water, forexample, a homopolymer of a polymerizable compound having one or moreacid groups and one or more polymerizable unsaturated bonds in themolecule, or a copolymer of two or more kinds thereof, and a copolymerof one or more polymerizable compounds having one or more unsaturatedbonds copolymerizable with these compounds and containing no acid group,can be used. Such compounds can be obtained by copolymerizing one ormore kinds of a low molecular compound having one or more acid groupsand one or more polymerizable unsaturated bonds in the molecule with oneor more polymerizable compounds having one or more unsaturated bondscopolymerizable with these compounds and containing no acid group.Examples of acids groups are, a —COOH group, a —SO₃H group, a —SO₂NHCO—group, a phenolic hydroxy group, a —SO₂NH— group, and a —CO—NH—CO—group. Among those, a high molecular compound having a —COOH group isparticularly preferred.

Preferably, the organic polymer binder in the color filter resistcomposition comprises an alkali soluble copolymer comprising, asaddition polymerizable monomer units, at least an unsaturated organicacid compound such as acrylic acid, methacrylic acid and the like. It ispreferred to use as a further co-monomer for the polymer binder anunsaturated organic acid ester compound such as methyl acrylate, ethyl(meth)acrylate, benzyl (meth)acrylate, styrene and the like to balanceproperties such as alkaline solubility, adhesion rigidity, chemicalresistance etc.

The organic polymer binder can either be a random co-polymer or ablock-co-polymer, for example, such as described in U.S. Pat. No.5,368,976.

Examples of the polymerizable compounds having one or more —COOH groupsand one or more polymerizable unsaturated bonds in a molecule are(meth)acrylic acid, 2-carboxyethyl (meth)acrylic acid, 2-carboxypropyl(meth)acrylic acid, crotonic acid, cinnamic acid,mono[2-(meth)acryloyloxyethyl]succinate,mono[2-(meth)acryloyloxyethyl]adipate,mono[2-(meth)acryloyloxyethyl]phthalate,mono[2-(meth)acryloyloxyethyl]hexahydrophthalate,mono[2-(meth)acryloyloxyethyl]maleate,mono[2-(meth)acryloyloxypropyl]succinate,mono[2-(meth)acryloyloxypropyl]adipate,mono[2-(meth)acryloyloxypropyl]phthalate,mono[2-(meth)acryloyloxypropyl]hexahydrophthalate,mono[2-(meth)acryloyloxypropyl]maleate,mono[2-(meth)acryloyloxybutyl]succinate,mono[2-(meth)acryloyloxybutyl]adipate,mono[2-(meth)acryloyloxybutyl]phthalate,mono[2-(meth)acryloyloxybutyl]hexahydrophthalate,mono[2-(meth)acryloyloxybutyl]maleate, 3-(alkylcarbamoyl)acrylic acid,α-chloroacrylic acid, maleic acid, monoesterified maleic acid, fumaricacid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride,and ω-carboxypolycaprolactone mono(meth)acrylate.

Vinylbenzenesulfonic acid and 2-(meth)acrylamide-2-methylpropanesulfonicacid are examples of the polymerizable compounds having one or more—SO₃H groups and one or more polymerizable unsaturated bonds.

N-methylsulfonyl (meth)acrylamide, N-ethylsulfonyl (meth)acrylamide,N-phenylsulfonyl (meth)acrylamide, and N-(p-methylphenylsulfonyl)(meth)acrylamide are examples of the polymerizable compounds having oneor more —SO₂NHCO— groups and one or more polymerizable unsaturatedbonds.

Examples of polymerizable compounds having one or more phenolic hydroxygroups and one or more polymerizable unsaturated bonds in a moleculeinclude hydroxyphenyl (meth)acrylamide, dihydroxyphenyl(meth)acrylamide, hydroxyphenyl-carbonyloxyethyl (meth)acrylate,hydroxyphenyloxyethyl (meth)acrylate, hydroxyphenylthioethyl(meth)acrylate, dihydroxyphenylcarbonyloxyethyl (meth)acrylate, dihydroxyphenyloxyethyl (meth)acrylate, and dihydroxy-phenylthioethyl(meth)acrylate.

Examples of the polymerizable compounds having one or more —SO₂NH—groups and one or more polymerizable unsaturated bonds in the moleculeinclude compounds represented by formula (a) or (b):

CH₂═CHA₁₀₀-Y₁₀₀-A₂₀₀-SO₂—NH-A₃  (a)

CH₂═CHA₄₀₀-Y₂₀₀-A₅₀₀-NH—SO₂-A₆₀₀  (b)

wherein Y₁₀₀ and Y₂₀₀ each represents —COO—, —CONA₇₀₀-, or a singlebond; A₁₀₀ and A₄₀₀ each represents H or CH₃; A₂₀₀ and A₅₀₀ eachrepresents C₁-C₁₂alkylene optionally having a substituent,cycloalkylene, arylene, or aralkylene, or C₂-C₁₂alkylene into which anether group and a thioether group are inserted, cycloalkylene, arylene,or aralkylene; A₃₀₀ and A₆₀₀ each represents H, C₁-C₁₂alkyl optionallyhaving a substituent, a cycloalkyl group, an aryl group, or an aralkylgroup; and A₇₀₀ represents H, C₁-C₁₂alkyl optionally having asubstituent, a cycloalkyl group, an aryl group, or an aralkyl group.

The polymerizable compounds having one or more —CO—NH—CO— group and oneor more polymerizable unsaturated bond include maleimide andN-acryloyl-acrylamide. These polymerizable compounds become the highmolecular compounds comprising a —CO—NH—CO— group, in which a ring isformed together with a primary chain by polymerization. Further, amethacrylic acid derivative and an acrylic acid derivative each having a—CO—NH—CO— group can be used as well. Such methacrylic acid derivativesand the acrylic acid derivatives include, for example, a methacrylamidederivative such as N-acetylmethacrylamide, N-propionylmethacrylamide,N-butanoylmethacrylamide, N-pentanoylmethacrylamide,N-decanoylmethacrylamide, N-dodecanoylmethacrylamide,N-benzoylmethacrylamide, N-(p-methylbenzoyl)methacryl-amide,N-(p-chlorobenzoyl)methacrylamide, N-(naphthyl-carbonyl)methacrylamide,N-(phenylacetyl)-methacrylamide, and 4-methacryloylaminophthalimide, andan acrylamide derivative having the same substituent as these. Thesepolymerizable compounds polymerize to be compounds having a —CO—NH—CO—group in a side chain.

Examples of polymerizable compounds having one or more polymerizableunsaturated bond and containing no acid group include a compound havinga polymerizable unsaturated bond, selected from esters of (meth)acrylicacid, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl(meth)acrylate, butyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate,benzyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl(meth)acrylate, glycerol mono(meth)acrylate, dihydroxypropyl(meth)acrylate, allyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl(meth)acrylate, methoxyphenyl (meth)acrylate, methoxyethyl(meth)acrylate, phenoxyethyl (meth)acrylate, methoxydiethyleneglycol(meth)acrylate, methoxytriethyleneglycol (meth)acrylate, methoxypropyl(meth)acrylate, methoxydipropyleneglycol (meth)acrylate, isobornylmeth(acrylate), dicyclopentadienyl (meth)acrylate,2-hydroxy-3-phenoxypropyl (meth)acrylate,tricyclo[5.2.1.0^(2,6)]decan-8-yl (meth)acrylate, aminoethyl(meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, aminopropyl(meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, glycidyl(meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl(meth)acrylate, 6,7-epoxyheptyl (meth)acrylate; vinyl aromaticcompounds, such as styrene, α-methylstyrene, vinyltoluene,p-chlorostyrene, polychlorostyrene, fluorostyrene, bromostyrene,ethoxymethyl styrene, methoxystyrene, 4-methoxy-3-methystyrene,dimethoxystyrene, vinylbenzyl methyl ether, vinylbenzyl glycidyl ether,indene, 1-methylindene; vinyl or allyl esters, such as vinyl acetate,vinyl propionate, vinyl butylate, vinyl pivalate, vinyl benzoate, vinyltrimethylacetate, vinyl diethylacetate, vinyl barate, vinyl caproate,vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinylbutoxyacetate, vinyl phenylacetate, vinyl acetate, vinyl acetoacetate,vinyl lactate, vinyl phenylbutylate, vinyl cyclohexylcarboxylate, vinylsalicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinylnaphthoate, allyl acetate, allyl propionate, allyl butylate, allylpivalate, allyl benzoate, allyl caproate, allyl stearate, allylacetoacetate, allyl lactate; vinyl or allyl ethers, such as vinyl methylether, vinyl ethyl ether, vinyl hexyl ether, vinyl octyl ether, vinylethylhexyl ether, vinyl methoxyethyl ether, vinyl ethoxyethyl ether,vinyl chloroethyl ether, vinyl hydroxyethyl ether, vinyl ethybutylether, vinyl hydroxyethoxyethyl ether, vinyl dimethylaminoethyl ether,vinyl diethylaminoethyl ether, vinyl butylaminoethyl ether, vinyl benzylether, vinyl tetrahydrofurfuryl ether, vinyl phenyl ether, vinyl tolylether, vinyl chlorophenyl ether, vinyl chloroethyl ether, vinyldichlorophenyl ether, vinyl naphthyl ether, vinyl anthryl ether, allylglycidyl ether; amide type unsaturated compounds, such as(meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dibutyl (meth)acrylamide, N,N-diethylhexyl(meth)acrylamide, N,N-dicyclohexyl (meth)acrylamide, N,N-diphenyl(meth)acrylamide, N-methyl-N-phenyl (meth)acrylamide,N-hydroxyethyl-N-methyl (meth)acrylamide, N-methyl (meth)acrylamide,N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-butyl(meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-heptyl(meth)acrylamide, N-octyl (meth)acrylamide, N-ethyhexyl(meth)acrylamide, N-hydroxyethyl (meth)acrylamidecyclohexyl, N-benzyl(meth)acrylamide, N-phenyl (meth)acrylamide, N-tolyl (meth)acrylamide,N-hydroxyphenyl (meth)acrylamide, N-naphthyl (meth)acrylamide,N-phenylsulfonyl (meth)acrylamide, N-methylphenylsulfonyl(meth)acrylamide and N-(meth)acryloylmorpholine, diacetone acrylamide,N-methylol acrylamide, N-butoxyacrylamide; polyolefin type compounds,such as butadiene, isoprene, chloroprene and the like;(meth)acrylonitrile, methyl isopropenyl ketone, maleimide,N-phenylmaleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide,N-cyclohexylmaleimide, N-alkylmaleimide, maleic anhydride, polystyrenemacromonomer, polymethyl (meth)acrylate macromonomer, polybutyl(meth)acrylate macromonomer; crotonates, such as butyl crotonate, hexylcrotonate, glycerine monocrotonate; and itaconates, such as dimethylitaconate, diethyl itaconate, dibutyl itaconate; and maleates orfumarates, such as dimethyl mareate, dibutyl fumarate.

Preferable examples of copolymers are copolymers of methyl(meth)acrylate and (meth)acrylic acid, copolymers of benzyl(meth)acrylate and (meth)acrylic acid, copolymers of methyl(meth)acrylate/, ethyl (meth)acrylate and (meth)acrylic acid, copolymersof benzyl (meth)acrylate, (meth)acrylic acid and styrene, copolymers ofbenzyl (meth)acrylate, (meth)acrylic acid and 2-hydroxyethyl(meth)acrylate, copolymers of methyl (meth)acrylate/, butyl(meth)acrylate, (meth)acrylic acid and styrene, copolymers of methyl(meth)acrylate, benzyl (meth)acrylate, (metha)crylic acid andhydroxyphenyl (meth)acrylate, copolymers of methyl (meth)acrylate,(meth)acrylic acid and polymethyl (meth)acrylate macromonomer,copolymers of benzyl (meth)acrylate, (meth)acrylic acid and polymethyl(meth)acrylate macromonomer, copolymers of tetrahydrofurfuryl(meth)acrylate, styrene and (meth)acrylic acid, copolymers of methyl(meth)acrylate, (meth)acrylic acid and polystyrene macromonomer,copolymers of benzyl (meth)acrylate, (meth)acrylic acid and polystyrenemacromonomer, copolymers of benzyl (meth)acrylate, (meth)acrylic acid,2-hydroxyethyl (meth)acrylate and polystyrene macromonomer, copolymersof benzyl (meth)acrylate, (meth)acrylic acid, 2-hydroxypropyl(meth)acrylate and polystyrene macromonomer, copolymers of benzyl(meth)acrylate, (meth)acrylic acid, 2-hydroxy-3-phenoxypropyl(meth)acrylate and polymethyl (meth)acrylate macromonomer, copolymers ofmethyl (meth)acrylate, (meth)acrylic acid, 2-hydroxyethyl (meth)acrylateand polystyrene macromonomer, copolymers of benzyl (metha)crylate,(meth)acrylic acid, 2-hydroxyethyl (meth)acrylate and polymethyl(meth)acrylate macromonomer, copolymers of N-phenylmaleimide, benzyl(meth)acrylate, (meth)acrylic acid and styrene, copolymers of benzyl(meth)acrylate, (meth)acrylic acid, N-phenylmaleimide,mono-[2-(meth)acryloyloxyethyl]succinate and styrene, copolymers ofallyl (meth)acrylate, (meth)acrylic acid, N-phenylmaleimide,mono-[2-(meth)acryloyloxyethyl]succinate and styrene, copolymers ofbenzyl (meth)acrylate, (meth)acrylic acid, N-phenylmaleimide, glycerolmono(meth)acrylate and styrene, copolymers of benzyl (meth)acrylate,ω-carboxypolycaprolactone mono(meth)acrylate, (meth)acrylic acid,N-phenylmaleimide, glycerol mono(meth)acrylate and styrene, andcopolymers of benzyl (meth)acrylate, (meth)acrylic acid,N-cyclohexylmaleimide and styrene.

There can be used as well hydroxystyrene homo- or co-polymers or anovolak type phenol resin, for example, poly(hydroxystyrene) andpoly(hydroxystyrene-covinylcyclohexanol), a novolak resin, a cresolnovolak resin, and a halogenated phenol novolak resin. Morespecifically, it includes, for example, the methacrylic acid copolymers,the acrylic acid copolymers, the itaconic acid copoymers, the crotonicacid co-polymers, the maleic anhydride co-polymers, for example, withstyrene as a co-monomer, and maleic acid copolymers, and partiallyesterified maleic acid copolymers each described in, for example, JP59-44615-B4 (the term “JP-B4” as used herein refers to an examinedJapanese patent publication), JP 54-34327-B4, JP 58-12577-B4, and JP54-25957-B4, JP 59-53836-A, JP 59-71048-A, JP 60-159743-A, JP60-258539-A, JP 1-152449-A, JP 2-199403-A, and JP 2-199404-A, and whichcopolymers can be further reacted with an amine, as e.g disclosed inU.S. Pat. No. 5,650,263; further, a cellulose derivative having acarboxyl group on a side chain can be used, and particularly preferredare copolymers of benzyl (meth)acrylate and (meth)acrylic acid andcopolymers of benzyl (meth)acrylate, (meth)acrylic acid and othermonomers, for example as described in U.S. Pat. No. 4,139,391, JP59-44615-B4, JP 60-159743-A and JP 60-258539-A.

With respect to those having carboxylic acid groups among the aboveorganic binder polymers, it is possible to react some or all of thecarboxylic acid groups with glycidyl(meth)acrylate or anepoxy(meth)acrylate to obtain photopolymerizable organic binder polymersfor the purpose of improving the photosensitivity, coating filmstrength, the coating solvent and chemical resistance and the adhesionto the substrate. Examples are disclosed in, JP 50-34443-B4 and JP50-34444-B4, U.S. Pat. No. 5,153,095, by T. Kudo et al. in J. Appl.Phys., Vol. 37 (1998), p. 3594-3603, U.S. Pat. No. 5,677,385, and U.S.Pat. No. 5,650,233.

The weight-average molecular weight of the binders is preferably 500 to1′000′000, e.g. 3′000 to 1′000′000, more preferably 5′000 to 400′000.

These compounds may be used singly or as a mixture of two or more kinds.The content of the binder in the light-sensitive resin composition ispreferably 10 to 95 weight %, more preferably 15 to 90 weight % based onthe whole solid matters.

Further, in the color filter the total solid component of each color maycontain an ionic impurity-scavenger, e.g. an organic compound having anepoxy group. The concentration of the ionic impurity scavenger in thetotal solid component generally is in the range from 0.1% by weight to10% by weight.

Examples of color filters, especially with respect to the abovedescribed combinations of pigments and ionic impurity scavenger aregiven in EP 320264. It is understood, that the photoinitiators accordingto the present invention, i.e. the compounds of the formula I, II, III,IV or V in the color filter formulations described in EP 320264 canreplace the triazine initiator compounds.

The compositions according to this invention can comprise additionally acrosslinking agent which is activated by an acid, for example asdescribed in JP 10-221843A, and a compound which generates acidthermally or by actinic radiation and which activates a crosslinkingreaction.

The compositions according to this invention can also comprise latentpigments which are transformed into finely dispersed pigments during theheat treatment of the latent pigment containing photosensitive patternor coating. The heat treatment can be performed after exposure or afterdevelopment of the latent pigment-containing photoimageable layer. Suchlatent pigments are soluble pigment precursors which can be transformedinto insoluble pigments by means of chemical, thermal, photolytic orradiation induced methods as described, for example, in U.S. Pat. No.5,879,855. This transformation of such latent pigments can be enhancedby adding a compound which generates acid at actinic exposure or byadding an acidic compound to the composition. Therefore, a color filterresist can also be prepared, which comprises a latent pigment in acomposition according to this invention.

Examples for color filter resists, the composition of such resists andthe processing conditions are given by T. Kudo et al., Jpn. J. Appl.Phys. Vol. 37 (1998) 3594; T. Kudo et al., J. Photopolym. Sci. Technol.Vol 9 (1996) 109; K. Kobayashi, Solid State Technol. November 1992, p.S15-S18; U.S. Pat. No. 5,368,976; U.S. Pat. No. 5,800,952; U.S. Pat. No.5,882,843; U.S. Pat. No. 5,879,855; U.S. Pat. No. 5,866,298; U.S. Pat.No. 5,863,678; JP 06-230212A; EP320264; JP 09-269410A; JP 10-221843A; JP01-090516A; JP 10-171119A, U.S. Pat. No. 5,821,016, U.S. Pat. No.5,847,015, U.S. Pat. No. 5,882,843, U.S. Pat. No. 5,719,008, EP881541,or EP902327.

The photoinitiators of the present invention can be used in color filterresists, for example, such as those given as examples above, or canpartially or fully replace the known photoinitiators in such resists. Itis understood by a person skilled in the art that the use of the newphotoinitiators of the present invention is not limited to the specificbinder resins, crosslinkers and formulations of the color filter resistexamples given hereinbefore but can be used in conjunction with anyradically polymerizable component in combination with a dye or colorpigment or latent pigment to form a photosensitive color filter ink orcolor filter resist.

Accordingly, subject of the invention also is a color filter prepared byproviding red, green and blue (RGB) colour elements and, optionally ablack matrix, all comprising a photosensitive resin and a pigment on atransparent substrate and providing a transparent electrode either onthe surface of the substrate or on the surface of the color filterlayer, wherein said photosensitive resin comprises a polyfunctionalacrylate monomer, an organic polymer binder and a photopolymerizationinitiator of formula I, II, III, IV or V as described above. The monomerand binder components, as well as suitable pigments are as describedabove. In the manufacture of color filters the transparent electrodelayer can either be applied on the surface of the transparent substrateor can be provided on the surface of the red, green and blue pictureelements and the black matrix. The transparent substrate is for examplea glass substrate which can additionally have an electrode layer on itssurface.

It is preferred to apply a black matrix between the color areas ofdifferent color in order to improve the contrast of a color filter.

The photosensitive compositions of the present invention, as alreadystated above, are also suitable for the preparation of the black matrixof color filters. Said black matrix composition for example comprises

a photoinitiator compound of the formula I, II, III, IV or V of thepresent invention,an organic binder, in particular an organic binder, which is an epoxyacrylate resin having a carboxyl group,a black coloring material,a polymer dispersant, in particular a polymer dispersant containing abasic functional group.

The person skilled in the art is familiar with such formulations.Examples of suitable black matrix compositions and the components (otherthan the photoinitiator) as described above are given in JP Patent No.3754065, the disclosure of which hereby is incorporated by reference.

Instead of forming a black matrix using a photosensitive composition andpatterning the black photosensitive composition photolithographically bypatternwise exposure (i.e. through a suitable mask) to form the blackpattern separating the red green and blue coloured areas on thetranparent substrate it is alternatively possible to use an inorganicblack matrix. Such inorganic black matrix can be formed from deposited(i.e. sputtered) metal (i.e. chromium) film on the transparent substrateby a suitable imaging process, for example utilizing photolithographicpatterning by means of an etch resist, etching the inorganic layer inthe areas not protected by the etch resist and then removing theremaining etch resist.

There are different methods known how and at which step in the colorfilter manufacturing process the black matrix can be applied. It caneither be applied directly on the transparent substrate prior toformation of the red, green and blue (RGB) colour filter as alreadymentioned above, or it can be applied after the RGB colour filter isformed on the substrate.

In a different embodiment of a color filter for a liqid crystal display,according to U.S. Pat. No. 626,796, the black matrix can also be appliedon the substrate opposite to the RGB color filter element-carryingsubstrate, which is separated from the former by a liquid crystal layer.

If the transparent electrode layer is deposited after applying the RGBcolor filter elements and—optionally—the black matrix, an additionalovercoat film as aprotective layer can be applied on the color filterlayer prior to deposition of the electrode layer, for example, asdescribed in U.S. Pat. No. 5,650,263.

To form an overcoat layer of a color filter, photosensitive resin orthermosetting resin compositions are employed. The photosensitivecomposition of the present invention can also be used to form suchovercoat layers, because a cured film of the composition is excellent inflatness, hardness, chemical and thermal resistance, transparencyespecially in a visible region, adhesion to a substrate, and suitabilityfor forming a transparent conductive film, e.g., an ITO film, thereon.In the production of a protective layer, there has been a demand thatunnecessary parts of the protective layer, for example on scribing linesfor cutting the substrate and on bonding pads of solid image sensorsshould be removed from the substrate as described in JP57-42009A,JP1-130103A and JP1-134306A. In this regard, it is difficult toselectively form a protective layer with good precision using theabove-mentioned thermosetting resins. The photosensitive composition,however, allows to easily remove the unnecessary parts of the protectivelayer by photolithography.

It is obvious to those skilled in the art, that the photosensitivecompositions of the present invention can be used for generating red,green and blue color pixels and a black matrix, for the manufacture of acolor filter, regardless of the above described differences inprocessing, regardless, of additional layers which can be applied andregardless of differences in the design of the color filter. The use ofa composition according to the present invention to form coloredelements shall not be regarded as limited by different designs andmanufacturing processes of such color filters.

The photo-sensitive composition of the present invention can suitably beused for forming a color filter but will not be limited to thisapplication. It is useful as well for a recording material, a resistmaterial, a protective layer, a dielectric layer, in displayapplications and display elements, a paint, and a printing ink.

The photosensitive compositions according to the invention are alsosuitable for manufacturing interlayer insulating layers or dielectriclayers in a liquid crystal display, and more particularly in areflection type liquid crystal display including an active matrix typedisplay having a thin film transistor (TFT) as a switching device, and apassive matrix type without a switching device.

In recent years, liquid crystal displays have, for example, been widelyused for pocket-type TV sets and terminal devices for communication byvirtue of its small thickness and light weight. A reflection type liquidcrystal display without necessity of using a back light is in particularin demand because it is ultra-thin and light-weight, and it cansignificantly reduce power consumption. However, even if a back light isremoved out of a presently available transmission type color liquidcrystal display and a light reflection plate is added to a lower surfaceof the display, it would cause a problem in that the efficiency ofutilizing lights is low, and it is not possible to have practicalbrightness. As a solution to this problem, there have been suggestedvarious reflection type liquid crystal displays for enhancing anefficiency of utilizing lights. For instance, a certain reflection typeliquid crystal display is designed to include a pixel electrode havingreflection function.

The reflection type liquid crystal display includes an insulatingsubstrate and an opposing substrate spaced away from the insulatingsubstrate. A space between the substrates is filled with liquidcrystals. A gate electrode is formed on the insulating substrate, andboth the gate electrode and the insulating substrate are covered with agate insulating film. A semiconductor layer is then formed on the gateinsulating film above the gate electrode. A source electrode and a drainelectrode are also formed on the gate insulating film in contact withthe semiconductor layer. The source electrode, the drain electrode, thesemiconductor layer, and the gate electrode cooperate with one anotherto thereby constitute a bottom gate type TFT as a switching device.

An interlayer insulating film is formed covering the source electrode,the drain electrode, the semiconductor layer, and the gate insulatingfilm therewith. A contact hole is formed throughout the interlayerinsulating film on the drain electrode. A pixel electrode made ofaluminum is formed on both the interlayer insulating film and an innersidewall of the contact hole. The drain electrode of the TFT iseventually in contact with the pixel electrode through the interlayerinsulating film. The interlayer insulating layer is generally designedto have a roughened surface by which the pixel electrode acts as areflection plate which diffuses lights to get a wider angle for viewing(angle of visibility).

The reflection type liquid crystal display remarkably enhances anefficiency of using lights by virtue that the pixel electrode acts as alight reflection plate.

In the above-mentioned reflection type liquid crystal display, theinterlayer insulating film is designed to have projections and recessesby photolithography. To form and control a fine shape of the projectionsand recesses in micrometer order for surface roughness and to formcontact holes, photolithography methods using positive and negativephotoresists are used. For these resists the compositions according tothe invention are especially suitable.

The photosensitive compositions according to the invention can furtherbe used for manufacturing spacers, which control a cell gap of theliquid crystal part in liquid crystal display panels. Since theproperties of light transmitted or reflected through the liquid crystallayer in a liquid crystal display are dependent on the cell gap, thethickness accuracy and uniformity over the pixel array are criticalparameters for the performance of the liquid crystal display unit. In aliquid crystal cell, the spacing between the substrates in the cell ismaintained constant by sparsely distributing glass or polymer spheresabout several micrometers in diameter as spacers between the substrates.The spacers are thus held between the substrates to maintain thedistance between the substrates at a constant value. The distance isdetermined by the diameter of the spacers. The spacers assure theminimum spacing between the substrates; i.e., they prevent a decrease indistance between the substrates. However, they cannot prevent thesubstrates from being separated apart from each other, i.e. the increasein distance between the substrates. Additionally, this method of usingspacer beads has problems of the uniformity in the diameter of spacerbeads and difficulty in the even dispersion of spacer beads on thepanel, as well as nonuniform orientation and decrease in brightnessand/or optical aperture depending on the location of spacers on pixelarray region. Liquid crystal displays having a large image display areahave recently been attracting much attention. However, the increase inthe area of a liquid crystal cell generally produces the distortion ofthe substrates constituting the cell. The layer structure of the liquidcrystal tends to be destroyed due to the deformation of the substrate.Thus, even when spacers are used for maintaining the spacing between thesubstrates constant, a liquid crystal display having a large imagedisplay area is unfeasible because the display experiences disturbances.Instead of the above spacer sphere dispersion method, a method offorming columns in the cell gap as spacers has been proposed. In thismethod, columns of a resin are formed as spacers in the region betweenthe pixel array region and the counter electrode to form a prescribedcell gap. Photosensitive materials having adhesive properties withphotolithography are commonly used, for instance, in the manufacturingprocess of color filters. This method is advantageous compared with theconventional method using spacer beads in the points that location,number and height of the spacers may be controlled freely. In recentyears, as the spread of the touch panel type liquid crystal displayssuch as mobile audio players and handheld game platforms, the mechanicalstress to liquid crystal panel tends to grow. The demand for spacer thatcontrols the cell gap to raise mechanical strength becomes strong thusthe multi-spacer method is used. According to the multi-spacer method,when cell gap narrows by pressure from the outside, adding tomain-spacer that controls the cell gap normally lower sub-spacersupports the cell gap against external stress. The multi-spacer canfollow the contraction of liquid crystal at low temperature conditionsby main-spacer and prevent to generate bubbles inside the liquidcrystal.

The multi-spacer which contains main-spacer and sub-spacer is formed inthe same step using, for example, a halftone mask as described inJPA-2011065133. The photosensitive compositions according to theinvention are eligible for manufacturing process using halftone mask.

In a color liquid crystal display panel, such spacers are formed in thenonimaging area under black matrix of color filter elements. Therefore,the spacers formed using photosensitive compositions do not decreasebrightness and optical aperture.

Photosensitive compositions for producing protective layer with spacersfor color filters are disclosed in JP 2000-81701A and dry film typephotoresists for spacer materials are also disclosed in JP 11-174459Aand JP 11-174464A. As described in the documents, the photosensitivecompositions, liquid and dry film photoresists, are comprising at leastan alkaline or acid soluble binder polymer, a radically polymerizablemonomer, and a radical initiator. In some cases, thermally crosslinkablecomponents such as epoxide and carboxylic acid may additionally beincluded.

The steps to form spacers using a photosensitive composition are asfollows:

a photosensitive composition is applied to the substrate, for instance acolor filter panel and after the substrate is prebaked, it is exposed tolight through a mask. Then, the substrate is developed with a developerand patterned to form the desired spacers. When the composition containssome thermosetting components, usually a postbaking is carried out tothermally cure the composition.

The photocurable compositions according to the invention are suitablefor producing spacers for liquid crystal displays (as described above)because of their high sensitivity.

The photosensitive compositions according to the invention are alsosuitable for manufacturing microlens arrays used in liquid crystaldisplay panels, image sensors and the like.

Microlenses are microscopic passive optical components that fit onactive optoelectronic devices such as detectors, displays, and lightemitting devices (light-emitting diodes, transversal and vertical cavitylasers) to improve their optical input or output quality. The areas ofapplications are wide and cover areas such as telecommunications,information technology, audio-visual services, solar cells, detectors,solid-state light sources, and optical interconnects.

Present optical systems use a variety of techniques to obtain efficientcoupling between microlenses and microoptical devices.

The microlens arrays are used for condensing illuminating light on thepicture element regions of a nonluminescent display device, such as aliquid crystal display devices, to increase the brightness of thedisplay, for condensing incident light or as a means for forming animage on the photoelectric conversion regions of a line image sensorused for example in facsimiles and the like to improve the sensitivityof these devices, and for forming an image to be printed on aphotosensitive means used in liquid crystal printers or light emittingdiode (LED) printers.

The most common application is their use to improve the efficiency ofphotodetector arrays of a solid-state image sensing device such as acharge coupled device (CCD). In a detector array, the collection of asmuch light as possible in each detector element or pixel is wanted. If amicrolens is put on top of each pixel, the lens collects incoming lightand focuses it onto an active area that is smaller than the size of thelens.

According to the prior-art, microlens arrays can be produced by avariety of methods; for each of them compositions according to thepresent invention may be employed.

(1) A method for obtaining convex lenses wherein a pattern of the lensesin a planar configuration is drawn on a thermoplastic resin by aconventional photolithographic technique or the like, and then thethermoplastic resin is heated to a temperature above the softening pointof the resin to have flowability, thereby causing a sag in the patternedge (so called “reflowing”) (see, e.g., JP 60-38989A, JP 60-165623A, JP61-67003A, and JP 2000-39503A). In this method, when the thermoplasticresin used is photosensitive, a pattern of the lenses can be obtained byexposure of this resin to light.

(2) A method for forming a plastic or glass material by the use of amold or a stamper. As lens material, a photocurable resin and athermosetting resin can be used in this method (see, e.g., WO99/38035).

(3) A method for forming convex lenses on the basis of a phenomenon inwhich when a photosensitive resin is exposed to light in a desiredpattern by the use of an aligner, unreacted monomers move from theunexposed regions to the exposed regions, resulting in a swell of theexposed regions (see, e.g., Journal of the Research Group in MicroopticsJapanese Society of Applied Physics, Colloquium in Optics, Vol. 5, No.2, pp. 118-123 (1987) and Vol. 6, No. 2, pp. 87-92(1988)).

On the upper surface of a supporting substrate, a photosensitive resinlayer is formed. Thereafter, with the use of a separate shading mask,the upper surface of the photosensitive resin layer is illuminated withlight from a mercury lamp or the like, so that the photosensitive resinlayer is exposed to the light. As a result, the exposed portions of thephotosensitive resin layer swell into the shape of convex lenses to formthe light condensing layer having a plurality of microlens.

(4) A method for obtaining convex lenses wherein a photosensitive resinis exposed to light by a proximity exposure technique in which aphotomask is not brought into contact with the resin, to cause a blur atthe pattern edge, so that the amount of photochemical reaction productsis distributed depending upon the degree of blurring at the pattern edge(see, e.g., JP 61-153602A).

(5) A method for generating a lens effect wherein a photosensitive resinis exposed to light with a particular intensity distribution to form adistribution pattern of refractive index depending upon the lightintensity (see, e.g., JP 60-72927A and JP 60-166946A). Thephotosensitive compositions according to the invention can be used inany one of the above-mentioned methods to form microlens arrays usingphotocurable resin compositions.

A particular class of techniques concentrates on forming microlenses inthermoplastic resins like photoresist. An example is published byPopovic et al. in the reference SPIE 898, pp. 23-25 (1988). Thetechnique, named reflow technique, comprises the steps of defining thelenses' footprint in a thermoplastic resin, e.g. by photolithography ina photosensitive resin like a photoresist, and subsequently heating thismaterial above its reflow temperature. The surface tension draws theisland of photoresist into a spherical cap with a volume equal to theoriginal island before the reflow. This cap is a plano-convex microlens.Advantages of the technique are, amongst others, the simplicity, thereproducibility, and the possibility of integration directly on top of alight-emitting or light-detecting optoelectronic device.

In some cases, an overcoat layer is formed on the patterned lens unitswith a rectangular shape prior to reflowing to avoid a sagging of theisland of the resin in the middle without reflow into a spherical cap inthe reflow step. The overcoat acts as a permanent protective layer. Thecoating layer is also made of a photosensitive composition. Microlensarrays can also be fabricated by the use of a mold or a stamper as, forexample, disclosed in EP0932256. A process of manufacturing the planarmicrolens array is as follows: a release agent is coated on a shapingsurface of a stamper on which convex portions are densely arranged, anda photocurable synthetic resin material having a high refractive indexis set on the shaping surface of the stamper. Next, the base glass plateis pushed onto the synthetic resin material, thereby spreading thesynthetic resin material, and the synthetic resin material is cured byirradiating with ultraviolet radiation or by heating and is shaped toform the convex microlenses. Thereafter the stamper is peeled off. Then,a photocurable synthetic resin material having a low refractive index isadditionally coated onto the convex microlenses as an adhesive layer anda glass substrate which is made into a cover glass plate is pushed ontothe synthetic resin material, thereby spreading the same. The syntheticresin material is then cured and finally the planar microlens array isformed.

As disclosed in U.S. Pat. No. 5,969,867, a similar method using a moldis applied for the production of a prism sheet, which is used as a partof backlight units for color liquid crystal display panels to enhancethe brightness. A prism sheet forming a prism row on one side is mountedon the light-emitting surface of the backlight. For fabricating a prismsheet, an active energy ray-curable composition is cast and spread in alens mold which is made of metal, glass or resin and forms the lensshape of the prism row, etc., after which a transparent substrate sheetis placed onto it and active energy rays from an active energyray-emitting source are irradiated through the sheet for curing. Theprepared lens sheet is then released from the lens mold to obtain thelens sheet.

The active energy ray-curable composition used to form the lens sectionmust have a variety of properties, including adhesion to the transparentsubstrate, and suitable optical characteristics.

Lenses at least with some photoresists in the prior art are notdesirable for some applications since the optical transmittance in theblue end of the optical spectrum is poor. Because the photocurablecompositions according to the invention have low yellowing properties,both thermally and photochemically, they are suitable for the productionof microlens arrays as described above.

The novel radiation-sensitive compositions are also suitable forphoto-lithographic steps used in the production process of plasmadisplay panels (PDP), particularly for the imaging forming process ofbarrier rib, phosphor layer and electrodes.

The PDP is a planar display for displaying images and information byvirtue of the emission of light by gas discharge. By the construction ofpanel and the method of operation, it is known in two types, i.e. DC(direct current) type and AC (alternating current) type.

By way of example, the principle of the DC type color PDP will bebriefly explained. In the DC type color PDP, the space interveningbetween two transparent substrates (generally glass plates) is dividedinto numerous minute cells by latticed barrier ribs interposed betweenthe transparent substrates. In the individual cells a discharge gas,such as He or Xe, is sealed. On the rear wall of each cell there is aphosphor layer which, on being excited by the ultraviolet lightgenerated by the discharge of the discharge gas, emits visible light ofthree primary colors. On the inner faces of the two substrates,electrodes are disposed as opposed to each other across the relevantcells. Generally, the cathodes are formed of a film of transparentelectroconductive material such as NESA glass. When a high voltage isapplied between these electrodes formed on the fore wall and the rearwall, the discharge gas which is sealed in the cells induces plasmadischarge and, by virtue of the ultraviolet light radiated consequently,incites the fluorescent elements of red, blue, and green colors to emitlights and effect the display of an image. In the full-color displaysystem, three fluorescent elements severally of the three primary colorsof red, blue, and green mentioned above jointly form one pictureelement.

The cells in the DC type PDP are divided by the component barrier ribsof a lattice, whereas those in the AC type PDP are divided by thebarrier ribs which are arranged parallel to each other on the faces ofthe substrates. In either case, the cells are divided by barrier ribs.These barrier ribs are intended to confine the luminous discharge withina fixed area to preclude false discharge or cross talk between adjacentdischarge cells and ensure ideal display.

The compositions according to the invention also find application forthe production of one- or more-layered materials for the image recordingor image reproduction (copies, reprography), which may be mono- orpolychromatic. Furthermore the materials are suitable for color proofingsystems. In this technology formulations containing microcapsules can beapplied and for the image production the radiation curing can befollowed by a thermal treatment. Such systems and technologies and theirapplications are for example disclosed in U.S. Pat. No. 5,376,459.

The compounds of the formula I, II, III, IV or V are also suitable asphotoinitiators in the holographic data storage application. Saidphotoinitiators generate radicals and initiate polymerization of monomerupon irradiation with blue laser radiation, suitable for holographicdata storage. The wavelength range of the blue laser is 390-420 nm,preferably 400-410 nm and particularly 405 nm. Holographic storagesystems (holographic recording media) are for example used to record andto retrieve a large amount of data with fast access time. Thephotoinitiators of the invention are for example in particular suitablefor systems as described for example in WO 03/021358.

The holographic data storage system is preferably comprised of a matrixnetwork of low-refractive index matrix precursors and high-refractiveindex photopolymerizable monomers.

The matrix precursor and photoactive monomer can be selected such that(a) the reaction by which the matrix precursor is polymerized during thecure is independent from the reaction by which the photoactive monomerwill be polymerized during writing of a pattern, e.g. data, and (b) thematrix polymer and the polymer resulting from polymerization of thephotoactive monomer (the photopolymer) are compatible with each other.The matrix is considered to be formed when the photorecording material,i.e. the matrix material plus the photoactive monomer, photoinitiatorand/or additives, exhibits an elastic modulus of at least about 10⁵ Pa,generally about 10⁵ Pa to about 10⁹ Pa.

The media matrix is formed by in-situ polymerization which yields ascross-linked network in the presence of the photopolymerizable monomerswhich remain “dissolved” and unreacted. The matrix containingun-reacted, photopolymerizable monomers can also be formed by othermeans, for example by using a solid-resin matrix material in which thephotoreactive, liquid monomer is homogeneously distributed. Then,monochromatic exposure generates the holographic pattern, whichaccording to the light intensity distribution, polymerizes thephotoreactive monomers in the solid pre-formed matrix. The unreactedmonomers (where light intensity was at a minimum) diffuse through thematrix, producing a modulation of the refractive index that isdetermined by the difference between the refractive indices of themonomer and the matrix and by the relative volume fraction of themonomer. The thickness of the recording layer is in the range of severalmicrometers up to a thickness of one millimeter. Because of such thickholographic data storage layers it is required that the photoinitiatorcombines high photoreactivity with low absorbance, in order to renderthe layer transparent at the laser wavelength to assure that the extentof photopolymerization is as little as possible dependent on theexposure depth into the recording layer.

It was found that the photoinitiators of the present invention combinehigh reactivity with low absorbance at 405 nm and are suitable for thisapplication. Dyes and sensitizers can also be added to the formulations.Suitable dyes and sensitizers for blue laser radiation are for examplecoumarines, xanthones, thioxanthones, see list above.

In particular relevant are thioxanthones, coumarins and benzophenones asmentioned under items 1., 2. and 3. in the list given above.

It was found that the photoinitiators allow photopolymerization ofmonomers in thick layers, such as required for holographic data storage,with high sensitivity and yield recording layers which are sensitive toblue laser radiation. The photoinitiators, when applied at aconcentration of 2-8 wt % in the photosensitive layer of 20 micronthickness yield an absorbance of the layer which comprises thephotoinitiator, of less than 0.4, preferably less than 0.2 at the laserwavelength.

The photoinitiators are in particular suitable for the preparation ofoptical articles (for example optical waveguides) or holographicrecording media e.g. comprising a polymer and an organic photoinitiatoras described above, having a maximum absorption at a UV wavelength inthe range of 340-450 nm, wherein the refractive index contrast adjustedsensitivity is greater than 3×10⁻⁶Δn/(mJ/cm²). For example, the polymeris formed by polymerizing a material comprising component 1 andcomponent 2, wherein component 1 comprises a NCO-terminated pre-polymerand component 2 comprises a polyol. Component 1 is, for example,diphenylmethane diisocyanate, toluene diisocyanate, hexamethylenediisocyanate, a derivative of hexamethylene diisocyanate, amethylenebiscyclohexylisocyanate, a derivative ofmethylenebiscyclohexylisocyanate. Component 2 is for example a polyol ofpropylene oxide. Preferably, the photoactive monomer is an acrylatemonomer. In such media the shrinkage induced by writing is usually lessthan 0.25%.

Photocuring further is of great importance for printings, since thedrying time of the ink is a critical factor for the production rate ofgraphic products, and should be in the order of fractions of seconds.UV-curable inks are particularly important for screen printing andoffset inks.

As already mentioned above, the novel mixtures are highly suitable alsofor producing printing plates. This application uses, for example,mixtures of soluble linear polyamides or styrene/butadiene and/orstyrene/isoprene rubber, polyacrylates or polymethyl methacrylatescontaining carboxyl groups, polyvinyl alcohols or urethane acrylateswith photopolymerizable monomers, for example acrylamides and/ormethacrylamides, or acrylates and/or methacrylates, and aphotoinitiator. Films and plates of these systems (wet or dry) areexposed over the negative (or positive) of the printed original, and theuncured parts are subsequently washed out using an appropriate solventor aqueous solutions.

Another field where photocuring is employed is the coating of metals, inthe case, for example, of the coating of metal plates and tubes, cans orbottle caps, and the photocuring of polymer coatings, for example offloor or wall coverings based on PVC. Examples of the photocuring ofpaper coatings are the colourless varnishing of labels, record sleevesand book covers.

Also of interest is the use of the novel photoinitiators for curingshaped articles made from composite compositions. The composite compoundconsists of a self-supporting matrix material, for example a glass fibrefabric, or alternatively, for example, plant fibres [cf. K.-P. Mieck, T.Reussmann in Kunststoffe 85 (1995), 366-370], which is impregnated withthe photocuring formulation. Shaped parts comprising compositecompounds, when produced using the novel compounds, attain a high levelof mechanical stability and resistance. The novel compounds can also beemployed as photocuring agents in moulding, impregnating and coatingcompositions as are described, for example, in EP7086. Examples of suchcompositions are gel coat resins, which are subject to stringentrequirements regarding curing activity and yellowing resistance, andfibre-reinforced mouldings, for example, light diffusing panels whichare planar or have lengthwise or crosswise corrugation. Techniques forproducing such mouldings, such as hand lay-up, spray lay-up, centrifugalcasting or filament winding, are described, for example, by P. H. Seldenin “Glasfaserverstärkte Kunststoffe”, page 610, Springer VerlagBerlin-Heidelberg-New York 1967. Examples of articles which can beproduced by these techniques are boats, fibre board or chipboard panelswith a double-sided coating of glass fibre-reinforced plastic, pipes,containers, etc. Further examples of moulding, impregnating and coatingcompositions are UP resin gel coats for mouldings containing glassfibres (GRP), such as corrugated sheets and paper laminates. Paperlaminates may be based on urea resins or melamine resins. Prior toproduction of the laminate, the gel coat is produced on a support (forexample a film). The novel photocurable compositions can also be usedfor casting resins or for embedding articles, for example electroniccomponents, etc.

The compositions and compounds according to the invention can be usedfor the production of holographies, waveguides, optical switches whereinadvantage is taken of the development of a difference in the index ofrefraction between irradiated and unirradiated areas.

The use of photocurable compositions for imaging techniques and for theoptical production of information carriers is also important. In suchapplications, as already described above, the layer (wet or dry) appliedto the support is irradiated imagewise, e.g. through a photomask, withUV or visible light, and the unexposed areas of the layer are removed bytreatment with a developer. Application of the photocurable layer tometal can also be carried out by electrodeposition. The exposed areasare polymeric through crosslinking and are therefore insoluble andremain on the support. Appropriate colouration produces visible images.Where the support is a metallized layer, the metal can, followingexposure and development, be etched away at the unexposed areas orreinforced by electroplating. In this way it is possible to produceelectronic circuits and photoresists. When used in image-formingmaterials the novel photoinitiators provide excellent performance ingenerating so called printout images, whereby a color change is induceddue to irradiation. To form such printout images different dyes and/ortheir leuco form are used and examples for such print out image systemscan be fount e.g. in WO96/41240, EP706091, EP511403, U.S. Pat. No.3,579,339 and U.S. Pat. No. 4,622,286.

The novel photoinitiator is also suitable for a photopatternablecomposition for forming a dielectric layer of a multilayer layer circuitboard produced by a sequential build-up process.

The invention, as described above, provides compositions, as well as aprocess, for producing pigmented and nonpigmented paints and varnishes,powder coatings, printing inks, printing plates, adhesives, pressuresensitive adhesives, dental compositions, gel coats, photoresists forelectronics, etch resists, both liquid and dry films, solder resists,resists to manufacture color filters for a variety of displayapplications (a color filter resist contains pigments, pigments and dyes(i.e. hybrid systems) or dyes alone), resists to generate structures inthe manufacturing processes of plasma-display panels (e.g. barrier rib,phosphor layer, electrode), electroluminescence displays and LCD (e.g.interlayer insulating layers, spacers, multi-spacers, microlens arrays),for encapsulating electrical and electronic components, for producingmagnetic recording materials, micromechanical parts, waveguides, opticalswitches, plating masks, colour proofing systems, glass fibre cablecoatings, screen printing stencils, three-dimensional objects by meansof stereolithography, image recording materials for holographicrecordings (e.g. for holographic data storage (HDS)), microelectroniccircuits, decolorizing materials, formulations containing microcapsules,photoresist materials for a UV and visible laser direct imaging systemand for forming dielectric layers in a sequential build-up layer of aprinted circuit board; wherein the process comprises irradiating acomposition as described above with electromagnetic radiation in therange from 150 to 600 nm, or with electron beam or with X-rays.

Substrates used for photographic information recordings include, forexample, films of polyester, cellulose acetate or polymer-coated papers;substrates for offset printing formes are specially treated aluminium,substrates for producing printed circuits are copper-clad laminates, andsubstrates for producing integrated circuits are, for example, siliconwafers. The layer thickness of the photosensitive layer for photographicmaterials and offset printing forms is generally from about 0.5 μm to 10μm, while for printed circuits it is from 0.1 μm to about 100 μm.Following the coating of the substrates, the solvent is removed,generally by drying, to leave a coat of the photoresist on thesubstrate.

Coating of the substrates can be carried out by applying to thesubstrate a liquid composition, a solution or a suspension. The choiceof solvents and the concentration depend principally on the type ofcomposition and on the coating technique. The solvent should be inert,i.e. it should not undergo a chemical reaction with the components andshould be able to be removed again, after coating, in the course ofdrying. Examples of suitable solvents are ketones, ethers and esters,such as methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone,cyclohexanone, N-methylpyrrolidone, dioxane, tetrahydrofuran,2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol,1,2-dimethoxyethane, ethyl acetate, n-butyl acetate, ethyl3-ethoxypropionate, 2-methoxypropylacetate, methyl-3-methoxypropionate,2-heptanone, 2-pentanone, and ethyl lactate. The solution is applieduniformly to a substrate by means of known coating techniques, forexample by spin coating, dip coating, knife coating, curtain coating,brushing, spraying, especially by electrostatic spraying, andreverse-roll coating, and also by means of electrophoretic deposition.It is also possible to apply the photosensitive layer to a temporary,flexible support and then to coat the final substrate, for example acopper-clad circuit board, or a glass substrate by transferring thelayer via lamination.

The quantity applied (coat thickness) and the nature of the substrate(layer support) are dependent on the desired field of application. Therange of coat thicknesses generally comprises values from about 0.1 μmto more than 100 μm, for example 0.1 μm to 1 cm, preferably 0.5 μm to1000 μm.

Following the coating of the substrates, the solvent is removed,generally by drying, to leave an essentially dry resist film of thephotoresist on the substrate.

The photosensitivity of the novel compositions can extend in generalfrom about 150 nm to 600 nm, for example 190-600 nm, (UV-vis region).Suitable radiation is present, for example, in sunlight or light fromartificial light sources. Consequently, a large number of very differenttypes of light sources are employed. Both point sources and arrays(“lamp carpets”) are suitable. Examples are carbon arc lamps, xenon arclamps, low-, medium-, high- and super high-pressure mercury lamps,possibly with metal halide dopes (metal-halogen lamps),microwave-stimulated metal vapour lamps, excimer lamps, superactinicfluorescent tubes, fluorescent lamps, argon incandescent lamps,electronic flashlights, photographic flood lamps, light emitting diodes(LED), electron beams and X-rays. The distance between the lamp and thesubstrate to be exposed in accordance with the invention may varydepending on the intended application and the type and output of lamp,and may be, for example, from 2 cm to 150 cm. Laser light sources, forexample excimer lasers, such as F₂ excimer lasers at 157 nm exposure,KrF excimer lasers for exposure at 248 nm and ArF excimer lasers forexposure at 193 nm are also suitable. Lasers in the visible region canalso be employed.

The term “imagewise” exposure includes both, exposure through aphotomask comprising a predetermined pattern, for example a slide, achromium mask, a stencil mask or a reticle, as well as exposure by meansof a laser or light beam, which for example is moved under computercontrol over the surface of the coated substrate and in this wayproduces an image. Suitable UV laser exposure systems for the purposeare, for example, provided by Etec and Orbotech (DP-100™ DIRECT IMAGINGSYSTEM). Other examples of laser light sources are, for example excimerlasers, such as F₂ excimer lasers at 157 nm exposure, KrF excimer lasersfor exposure at 248 nm and ArF excimer lasers for exposure at 193 nm.Further suitable are solid state UV lasers (e.g. Gemini from ManiaBarco,DI-2050 from PENTAX) and violet laser diodes with 405 nm output(DI-2080, DI-PDP from PENTAX). Lasers in the visible region can also beemployed. And the computer-controlled irradiation can also be achievedby electron beams. It is also possible to use masks made of liquidcrystals that can be addressed pixel by pixel to generate digitalimages, as is, for example, described by A. Bertsch, J. Y. Jezequel, J.C. Andre in Journal of Photochemistry and Photobiology A: Chemistry1997, 107, p. 275-281 and by K.-P. Nicolay in Offset Printing 1997, 6,p. 34-37.

Following the imagewise exposure of the material and prior todevelopment, it may be advantageous to carry out thermal treatment for ashort time. After the development a thermal post bake can be performedto harden the composition and to remove all traces of solvents. Thetemperatures employed are generally 50-250° C., preferably 80-220° C.;the duration of the thermal treatment is in general between 0.25 and 60minutes.

The photocurable composition may additionally be used in a process forproducing printing plates or photoresists as is described, for example,in DE4013358. In such a process the composition is exposed for a shorttime to visible light with a wavelength of at least 400 nm, without amask, prior to, simultaneously with or following imagewise irradiation.

After the exposure and, if implemented, thermal treatment, the unexposedareas of the photosensitive coating are removed with a developer in amanner known per se.

As already mentioned, the novel compositions can be developed by aqueousalkalis or organic solvents. Particularly suitable aqueous-alkalinedeveloper solutions are agueous solutions of tetraalkylammoniumhydroxides or of alkali metal silicates, phosphates, hydroxides andcarbonates. Minor quantities of wetting agents and/or organic solventsmay also be added, if desired, to these solutions. Examples of typicalorganic solvents, which may be added to the developer liquids in smallquantities, are cyclohexanone, 2-ethoxyethanol, toluene, acetone andmixtures of such solvents. Depending on the substrate also solvents,e.g. organic solvents, can be used as developer, or, as mentioned abovemixtures of aqueous alkalis with such solvents. Particularly usefulsolvents for solvent development include methanol, ethanol, 2-propanol,1-propanol, butanol, diacetone alcohol, ethylene glycol monomethylether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butylether, diethyleneglycol dimethyl ether, propyleneglycol monomethyl etheracetate, ethyl-3-ethoxypropionate, methyl-3-methoxypropionate, n-butylacetate, benzyl alcohol, acetone, methyl ethyl ketone, cyclopentanone,cyclohexanone, 2-heptanone, 2-pentanone, epsilon-caprolactone,gamma-butylolactone, dimethylformamide, dimethylacetamide,hexamethylphosphoramide, ethyl lactate, methyl lactate,epsilon-caprolactam, and N-methyl-pyrrolidinone. Optionally, water canbe added to these solvents up to a level at which still a clear solutionis obtained and at which sufficient solubility of the unexposed areas ofthe light sensitive composition is maintained.

The invention therefore also provides a process for thephotopolymerization of compounds containing ethylenically unsaturateddouble bonds, i.e. monomeric, oligomeric or polymeric compoundscontaining at least one ethylenically unsaturated double bond, whichcomprises adding to these compounds at least one photoinitiator of theformula I, II, III, IV or V as described above and irradiating theresulting composition with electromagnetic radiation, in particularlight of the wavelength 150 to 600 nm, in particular 190-600 nm, withelectron beam, or with X-rays.

In other words, adding to these compounds containing ethylenicallyunsaturated double bonds at least one photoinitiator of the formula I,II, III, IV or V as described above and irradiating the resultingcomposition with electromagnetic radiation, in particular light of thewavelength 150 to 600 nm, in particular 190-600 nm, with electron beam,or with X-rays.

The invention further provides a coated substrate which is coated on atleast one surface with a composition as described above, and describes aprocess for the photographic production of relief images, in which acoated substrate is subjected to imagewise exposure and then theunexposed portions are removed with a developer. Imagewise exposure maybe effected by irradiating through a mask or by means of a laser orelectron beam as already described above. Of particular advantage inthis context is the laser beam exposure already mentioned above.

The compounds of the invention have a good thermal stability, lowvolatility, good storage stability and high solubility, and are alsosuitable for photopolymerisations in the presence of air (oxygen).Further, they cause only low yellowing in the compositions afterphotopolymerization.

The examples which follow illustrate the invention in more detail,without restriciting the scope said examples only. Parts and percentagesare, as in the remainder of the description and in the claims, byweight, unless stated otherwise. Where alkyl radicals having more thanthree carbon atoms are referred to in the examples without any mentionof specific isomers, the n-isomers are meant in each case.

EXAMPLE 1 Synthesis of[9-(2-ethyl-hexyl)-6-(acetoxyimino-o-tolyl-methyl)-9H-carbazol-3-yl]-(2,4,6-trimethyl-phenyl)-methanone1.a Synthesis of[9-(2-ethyl-hexyl)-6-(2-methyl-benzoyl)-9H-carbazol-3-yl]-(2,4,6-trimethyl-phenyl)-methanone

To 9-(2-ethyl-hexyl)-9H-carbazole (1.40 g; 5.00 mmol) in CH₂Cl₂ (50 mL)are added 2,4,6-trimethylbenzoyl chloride (0.91 g; 5.00 mmol) and AlCl₃(0.69 g; 5.15 mmol) at 0° C. After stirring for 3 h at 0° C., AlCl₃(0.69 g; 5.15 mmol) and o-toluoyl chloride (0.80 g; 5.15 mmol) are addedat 0° C., and the mixture is stirred at room temperature overnight. Thereaction mixture is poured into ice-water, and the crude product isextracted twice with CH₂Cl₂. The combined organic layer is washed withH₂O and brine, dried over MgSO₄, and concentrated and dried in vacuo togive a beige solid as a crude product (2.08 g). The product is used forthe next reaction without further purification. The structure isconfirmed by ¹H-NMR spectrum (CDCl₃). δ[ppm]: 0.81 (t, 3H), 0.92 (t,3H), 1.21-1.42 (m, 8H), 2.05 (m, 1H), 2.13 (s, 6H), 2.34 (s, 3H), 4.20(m, 2H), 6.94 (s, 2H), 7.27-7.37 (m, 4H), 7.41-7.45 (m, 3H), 7.98-8.02(m, 2H), 8.56 (br, 1H), 8.57 (s, 1H).

1.b Synthesis of[9-(2-ethyl-hexyl)-6-(hydroxyimino-o-tolyl-methyl)-9H-carbazol-3-yl]-(2,4,6-trimethyl-phenyl)-methanone

To[9-(2-ethyl-hexyl)-6-(2-methyl-benzoyl)-9H-carbazol-3-yl]-(2,4,6-trimethyl-phenyl)-methanone(2.00 g; 3.78 mmol) in pyridine (10 mL) are added hydroxylammoniumchloride (0.52 g; 7.55 mmol) at 120° C., and then the mixture is stirredat 120° C. overnight. After it is cooled at room temperature, thereaction mixture is poured into water, and the crude product isextracted twice with CH₂Cl₂. The combined organic layer is washed withwater and brine and dried over MgSO₄. After CH₂Cl₂ is removed byconcentration, the crude product is recrystallized with a mixed solventof CH₂Cl₂ (2 mL) and n-hexane (10 mL) to give a beige solid. It iscollected by filtration, and washed with n-hexane, and then it is driedto give a beige solid (0.66 g; 31%). The product is composed of anisomeric mixture, and the structure is confirmed by ¹H-NMR spectrum(CDCl₃). δ [ppm]: 0.82 (m), 1.25 (m), 2.02 (m), 2.12 (s), 2.25 (s), 2.36(s), 4.20 (m), 6.92 (s), 7.20 (d), 7.33-7.745 (m), 7.65 (br), 7.89 (br),8.16 (s), 8.55 (br).

1.c Synthesis of[9-(2-Ethyl-hexyl)-6-(acetoxyimino-o-tolyl-methyl)-9H-carbazol-3-yl]-(2,4,6-trimethyl-phenyl)-methanone

To[9-(2-ethyl-hexyl)-6-(hydroxyimino-o-tolyl-methyl)-9H-carbazol-3-yl]-(2,4,6-trimethyl-phenyl)-methanonein AcOEt (ethyl acetate) (5 mL) are added triethylamine (0.36 g; 3.54mmol) and acetyl chloride (0.28 g; 3.54 mmol) at 0° C. Then the mixtureis stirred at 0° C. for 1 h. The reaction mixture is poured intoice-water, and the crude product is extracted with AcOEt. The combinedorganic layer is washed with H₂O and brine, dried over MgSO₄, andconcentrated and dried in vacuo to give a yellow resin as a crudeproduct. The crude product is composed of an isomeric mixture accordingto ¹H-NMR spectrum. The crude product is purified by columnchromatography on silica gel eluting with a mixed solvent of CH₂Cl₂ andn-hexane (4:1) to obtain a pale yellow solid (0.49 g, 69%). Thestructure is confirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]: 0.82 (t,3H), 0.92 (t, 3H), 2.02 (m, 1H9, 2.06 (s, 3H), 2.12 (s, 6H), 2.19 (s,3H), 2.36 (s, 3H), 4.20 (m, 2H), 6.93 (s, 2H), 7.14 (dd, 1H), 7.30-7.43(m, 5H), 7.71 (br, 1H), 8.00 (br, 1H), 8.32 (br, 1H), 8.52 (br, 1H).

EXAMPLES 2-11

In case of the compounds of example 2-5, the corresponding di-ketoneintermediates are prepared according to the procedure as discribed inexample 1.a with the corresponding aroyl chloride using9-(2-ethyl-hexyl)-9H-carbazole or 9-ethyl-9H-carbazole as a startingmaterial, and then the oxime and the oxime ester are prepared accordingto the procedures as disclosed in examples 1.b and 1.c. In case of thecompound of example 6, the corresponding di-ketone is prepared byreaction of[6-(2-chloromethyl-benzoyl)-9-ethyl-9H-carbazol-3-yl]-(2,4,6-trimethyl-phenyl)-methanonewith ethyl mercaptoacetate, and then the oxime and the oxime ester areprepared according to the procedures as disclosed in examples 1.b and1.c. The corresponding diketone intermediates of the compouns ofexamples 7-11 are prepared by reacting mono- or di-fluorinated diketoneintermediate with the corresponding nucleophiles. Then, the oxime andthe oxime ester are prepared according to the procedures as disclosed inexamples 1.b and 1.c. The compounds of the examples 2, 3, 5, 6, 7, 9 and11 are obtained as an isomeric mixture, but the compounds of the otherexamples are obtained as a single component.

TABLE 1

¹H-NMR Example Ar₁ Ar₂ R δ [ppm]  2

1.48 (t, 3H), 2.12 (s, 6H), 2.18 (s, 3H), 2.36 (s, 3H), 4.38 (q, 2H),6.93 (s, 2H), 7.13 (d, 1H), 7.28-7.45 (m, 5H), 7.73 (br, 1H), 7.99 (br,1H), 8.34 (br, 1H), 8.52 (br, 1H)  3

0.80-0.98 (m), 1.18-1.48 (m), 2.01 (s), 2.05 (m), 2.16 (s), 2.18 (s),2.22 (s), 3.72 (s), 4.17 (m), 6.67 (d), 7.14 (d), 7.20-7.44 (m), 7.59(d), 7.66 (d), 7.97 (d), 8.05 (d), 8.21 (s), 8.33 (s), 8.54 (s), 8.61(s)  4

0.78-0.96 (m), 1.18-1.45 (m), 2.03 (m), 2.10 (s), 2.12 (s), 2.35 (s),4.19 (m), 6.93 (s), 7.37-7.44 (m), 7.56 (d), 7.68 (br), 8.00 (br), 8.24(br), 8.40 (d), 8.52 (br)  5

0.82-0.98 (m), 1.20-1.48 (m), 2.05 (s), 2.06 (s), 2.13 (s), 2.16 (s),2.23 (s), 2.36 (s), 4.22 (m), 6.93 (s), 7.15 (d), 7.23-7.45 (m),7.46-7.59 (m), 7.95 (br), 8.20 (s), 8.41 (br), 8.56 (br)  6

1.21 (t), 1.46 (t), 2.05 (s), 2.12 (s), 2.36 (s), 3.06 (d), 3.71 (d),4.09 (q), 4.40 (m), 6.93 (s), 7.20 (d), 7.36-7.42 (m), 7.50 (t), 7.61(d), 7.73 (br), 8.00 (br), 8.22 (s), 8.35 (br), 8.52 (br)  7

0.81-1.02 (m), 1.10-1.52 (m), 2.04 (m), 2.08 (s), 2.12 (s), 2.16 (s),2.35 (s), 3.24 (m), 3.32 (m), 3.86 (m), 3.89 (m), 4.19 (m), 4.22 (m),6.84 (d), 6.92 (s), 6.96 (d), 6.96 (d), 7.34-7.54 (m), 7.74 (br), 7.98(s), 8.04 (br), 8.25 (s), 8.48 (br)  8

1.46 (t), 2.08 (s), 2.12 (s), 2.36 (s), 3.18 (s), 3.48 (t), 3.50 (s),3.81 (t), 4.04 (t), 4.21 (t), 4.38 (q), 6.60 (d), 6.67 (s), 6.93 (s),7.04 (d), 7.36 (d), 7.40 (d), 7.74 (br), 8.04 (br), 8.33 (s), 8.50 (br) 9

1.48 (t), 2.12 (s), 2.19 (s), 2.36 (s), 4.11 (t), 4.42 (q), 5.03 (m),6.88 (d), 6.93 (s), 7.18 (t), 7.41 (d), 7.48 (d), 7.49 (d), 7.61 (d),7.72 (d), 7.93 (br), 8.08 (s), 8.55 (br) 10

1.46 (t), 2.07 (s), 2.09 (s), 2.12 (s), 2.36 (s), 4.38-4.45 (m), 6.93(s), 7.07 (d), 7.20 (d), 7.38 (d), 7.53 (m), 7.78 (br), 7.96 (br), 8.25(br), 8.55 (br) 11

1.44 (t), 2.06 (s), 2.11 (s), 2.19 (s), 2.36 (s), 3.90 (t), 4.20-4.50(m), 6.93 (s), 7.07 (d), 7.20 (d), 7.30- 7.56 (m), 7.60 (d), 7.63 (d),7.82 (br), 8.12 (br), 8.25 (br), 8.56 (br)

EXAMPLE 12[1-[4-[3-[N-acetoxy-C-phenyl-carbonimidoyl]-6-(2,4,6-trimethylbenzo-yl)carbazol-9-yl]phenyl]ethylideneamino]acetate12.a 1-(4-carbazol-9-ylphenyl)ethanone

To carbazole (5.02 g; 30.0 mmol) in DMSO (50 mL) is added4-fluoroacetophenone (3.45 g; 25.0 mmol) and K₂CO₃ (10.4 g; 75.2 mmol),and the mixture is stirred at 135° C. overnight. The mixture is pouredinto water to afford a precipitate, which is isolated by filtration andwashed with water. The crude product thus obtained is further purifiedby recrystallization from TBME (tert-butyl methyl ether), giving theproduct as a light brown solid. The structure is confirmed by the ¹H-NMRspectrum (CDCl₃). δ [ppm]: 2.71 (s), 7.32 (d), 7.41-7.50 (m), 7.72 (d),8.15 (d), 8.21 (d).

12.b1-[4-[3-benzoyl-6-(2,4,6-trimethylbenzovI)carbazol-9-yl]phenyl]ethanone

To 1-(4-carbazol-9-ylphenyl)ethanone (5.73 g; 20.0 mmol) in CH₂Cl₂ (50mL) are added 2,4,6-trimethylbenzoyl chloride (3.84 g; 21.0 mmol) andAlCl₃ (5.60 g, 42.0 mmol) at 0° C. After stirring over night at roomtemperature, AlCl₃ (2.80 g, 21.0 mmol) and benzoyl chloride (2.95 g,21.0 mmol) are added at 0° C., and the mixture is stirred at roomtemperature overnight. The reaction mixture is poured into ice-water,and the crude product is extracted twice with CH₂Cl₂. The combinedorganic layer is washed with water and brine, dried over MgSO₄. AfterCH₂Cl₂ is removed by concentration, the crude product is purified bycolumn chromatography on silica gel eluting with a mixed solvent ofCH₂Cl₂ and n-hexane (1:1) to obtain a pale white solid (2.25 g, 21%).The structure is confirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]: 2.14(s), 2.39 (s), 2.72 (s), 6.94 (s), 7.43-7.58 (m), 7.58-7.68 (m),7.70-7.80 (m), 7.82-7.89 (m), 7.97 (d), 8.02 (d), 8.11 (d), 8.26 (d),8.28 (d), 8.60 (br), 8.64 (s).

12.c[9-[4-[N-hydroxy-C-methyl-carbonimidoyl]phenyl]-6-[N-hydroxy-C-phenyl-carbonimidoyl]carbazol-3-yl]-(2,4,6-trimethylphenvIlmethanone

To1-[4-[3-benzoyl-6-(2,4,6-trimethylbenzoyl)carbazol-9-yl]phenyl]ethanone(1.10 g; 2.00 mmol) in pyridine (5 mL) is added hydroxylammoniumchloride (0.81 g; 12.0 mmol) at 100° C., and then the mixture is stirredat 100° C. overnight. After it is cooled at room temperature, thereaction mixture is poured into water, and the crude product isextracted twice with AcOEt (ethyl acetate). The combined organic layeris washed with water and brine and dried over MgSO₄. After AcOEt isremoved by concentration, the crude product is purified by columnchromatography on silica gel eluting with a mixed solvent of AcOEt andn-hexane (1:2) to obtain a pale white solid (2.48 g, 22%). The productis composed of an isomeric mixture, and the structure is confirmed by¹H-NMR spectrum (CDCl₃). δ [ppm]: 2.12 (s), 2.33 (s), 2.40 (s), 6.88(s), 7.30-7.66 (m), 7.88 (d), 7.90 (d), 7.99 (br), 8.20 (s), 8.55 (br).

12.d[1-[4-[3-[N-acetoxy-C-phenyl-carbonimidoyl]-6-(2,4,6-trimethylbenzoyl)carbazol-9-yl]phenyl]ethylideneamino]acetate

To[9-[4-[N-hydroxy-C-methyl-carbonimidoyl]phenyl]-6-[N-hydroxy-C-phenyl-carbonimidoyl]carbazol-3-yl]-(2,4,6-trimethylphenyl)methanone(0.24 g; 0.42 mmol) in AcOEt (5 mL) are added triethylamine (0.43 g;4.24 mmol) and acetyl chloride (0.34 g; 4.24 mmol) at 0° C. Then themixture is stirred at 0° C. for 3 hours. The reaction mixture is pouredinto ice-water, and the crude product is extracted with AcOEt. Thecombined organic layer is washed with H₂O and brine, dried over MgSO₄,and concentrated. The crude product is purified by column chromatographyon silica gel eluting with a mixed solvent of AcOEt and n-hexane (1:1)to obtain a pale yellow solid (0.28 g, 74%). The product is composed ofan isomeric mixture, and the structure is confirmed by ¹H-NMR spectrum(CDCl₃). δ [ppm]: 2.11 (s), 2.13 (s), 2.31 (s), 2.32 (s), 2.35 (s), 2.36(s), 2.50 (s), 2.51 (s), 6.93 (s), 6.94 (s), 7.31-7.54 (m), 7.58-7.69(m), 7.98 (br), 8.01-8.08 (m), 8.41 (s), 8.55 (br).

EXAMPLE 13[[2-[6-[2-[N-acetoxy-C-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]-carbonimidoyl]phenoxy]-2,2,3,3,4,4,5,5-octafluoro-hexoxy]phenyl]-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]methylene]aminoacetate 13.a[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]-(2-fluorophenyl)methanone

To 9-ethyl-9H-carbazole (8.50 g; 43.5 mmol) in CH₂Cl₂ (200 mL) are added2,4,6-trimethylbenzoyl chloride (8.35 g; 45.7 mmol) and AlCl₃ (6.37 g;47.8 mmol) at 0° C. After stirring for 20 minutes, AlCl₃ (6.53 g; 48.9mmol) is added and 2-fluorobenzoyl chloride (7.26 g; 45.7 mmol) is addeddropwise, and then the mixture is stirred at room temperature for 5hours. The reaction mixture is poured into ice-water, and the crudeproduct is extracted twice with CH₂Cl₂. The combined organic layer iswashed with water and brine, dried over MgSO₄. After 100 mL of n-hexaneis added there, CH₂Cl₂ is removed by concentration to give a whitesolid. It is collected by filtration, and washed with n-hexane, and thenit is dried to give a white solid (17.82 g; 88%). The structure isconfirmed by ¹H-NMR spectrum (CDCl₃). □δ [ppm]: 1.49 (t), 2.13 (s), 2.38(s), 4.42 (q), 6.94 (s), 7.21 (t), 7.32 (t), 7.44 (d), 7.46 (d),7.53-7.62 (m), 8.25 (br), 8.04 (d), 8.56 (br), 8.60 (s); ¹⁹F-NMRspectrum (CDCl₃). δ [ppm]: −111.75.

13.b[2-[6-[2-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazole-3-carbonyl]phenoxy]-2,2,3,3,4,4,5,5-octafluoro-hexoxy]phenyl]-[9-ethyl-6-(2,4,6-trimethylbenzoyl)-carbazol-3-yl]methanone

To[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]-(2-fluorophenyl)methanone(1.86 g; 4.01 mmol) in pyridine (10 mL) are added2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol (0.47 g; 1.8 mmol) and sodiumhydroxide (0.24 g; 6.0 mmol) at 80° C. The mixture is stirred overnight.The reaction mixture is poured into ice-water, the crude product isextracted twice with AcOEt. The combined organic layer is washed withwater and brine, dried over MgSO₄. After AcOEt is removed byconcentration, the crude product is recrystallized with a mixed solventof CH₂Cl₂ (2 mL) and n-hexane (10 mL) to give a beige solid. It iscollected by filtration, and washed with n-hexane, and then it is driedto give a beige solid (0.44 g; 21%). The product is composed of anisomeric mixture, and the structure is confirmed by ¹H-NMR spectrum(CDCl₃). δ [ppm]: 1.42 (t), 2.10 (s), 2.37 (s), 4.22 (t), 4.35 (q), 6.92(s), 7.19 (t), 7.34-7.50 (m), 7.92 (s), 7.94 (br), 8.50 (s), 8.51 (br).

13.c[9-ethyl-6-[C-[2-[6-[2-[C-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]-N-hydroxy-carbonimidoyl]phenoxy]-2,2,3,3,4,4,5,5-octafluoro-hexoxy]phenyl]-N-hydroxy-carbonimidoyl]carbazol-3-yl]-(2,4,6-trimethylphenyl)methanone

To[2-[6-[2-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazole-3-carbonyl]phenoxy]-2,2,3,3,-4,4,5,5-octafluoro-hexoxy]phenyl]-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]methanone (0.44 g; 0.38 mmol) in pyridine (5 mL)are added hydroxylammonium chloride (0.16 g; 2.30 mmol) at 100° C., andthen the mixture is stirred at 100° C. overnight. After it is cooled atroom temperature, the reaction mixture is poured into water, and thecrude product is extracted twice with AcOEt (ethyl acetate). Thecombined organic layer is washed with water and brine and dried overMgSO₄. After AcOEt is removed by concentration, the crude product ispurified by column chromatography on silica gel eluting with a mixedsolvent of AcOEt and n-hexane (1:1) to obtain a pale white solid (0.28g, 63%). The product is composed of an isomeric mixture, and thestructure is confirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]: 1.23 (t),2.11 (m), 2.32 (s), 2.35 (s), 4.32-4.64 (m), 6.91 (s), 7.06-7.42 (m),7.42 (d), 7.46-7.56 (m), 7.75 (br), 7.80-7.91 (m), 7.93 (s), 8.00 (s),8.37 (s), 8.63 (br).

13.d[[2-[6-[2-[N-acetoxy-C-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]carbonimidoyl]phenoxy]-2,2,3,3,4,4,5,5-octafluoro-hexoxy]phenyl]-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]methylene]aminoacetate

To[9-ethyl-6-[C-[2-[6-[2-[C-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]-N-hydroxy-carbonimidoyl]phenoxy]-2,2,3,3,4,4,5,5-octafluoro-hexoxy]phenyl]-N-hydroxy-carbonimidoyl]carbazol-3-yl]-(2,4,6-trimethylphenyl)methanone(0.28 g; 0.24 mmol) in AcOEt (5 mL) are added triethylamine (0.24 g; 2.4mmol) and acetyl chloride (0.19 g; 2.4 mmol) at 0° C. Then the mixtureis stirred at 0° C. for 4 hours. The reaction mixture is poured intoice-water, and the crude product is extracted with AcOEt. The combinedorganic layer is washed with H₂O and brine, dried over MgSO₄, andconcentrated. The crude product is purified by column chromatography onsilica gel eluting with a mixed solvent of AcOEt and n-hexane (1:1) toobtain a pale yellow solid (0.16 g, 54%). The product is composed of anisomeric mixture, and the structure is confirmed by ¹H-NMR spectrum(CDCl₃). δ [ppm]: 1.22 (m), 2.01 (s), 2.08 (s), 2.11 (s), 2.16 (s), 2.34(s), 2.35 (s), 4.05 (t), 4.33 (m), 6.80 (m), 6.92 (s), 6.98 (m), 7.16(s), 7.28-7.54 (m), 7.60 (d), 7.64 (d), 7.71 (br), 7.95 (br), 8.02 (s),8.28 (br), 8.52 (br).

EXAMPLE 14[[2-[6-[2-[N-acetoxy-C-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]carbonimidoyl]phenoxy]hexoxy]phenyl]-[9-ethyl-6-(2,4,6-trimethylbenzoyl)-carbazol-3-yl]methylene]aminoacetate

The corresponding dimer intermediate of diketone is prepared accordingto the procedure as disclosed in example 13.b with 1,6-hexanediolinstead of 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, and then the oximeand oxime ester are prepared the same procedure as 13.c and 13.drespectively. The structure is confirmed by ¹H-NMR spectrum (CDCl₃). δ[ppm]: 0.78 (m), 1.15 (m), 1.39 (t), 2.00 (s), 2.10 (s), 2.35 (s), 3.60(m), 4.31 (q), 6.85 (d), 6.92 (s), 7.03 (t), 7.12 (d), 7.28 (d),7.32-7.42 (m), 7.65 (br), 7.96 (br), 8.30 (br), 8.50 (br).

EXAMPLE 15[[4-[6-[4-[N-acetoxy-C-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]-carbonimidoyl]phenoxy]-2,2,3,3,4,4,5,5-octafluoro-hexoxy]phenyl]-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]methylene]aminoacetate

The corresponding diketone intermediate is prepared according to theprocedure as disclosed ini example 13.a with 4-fluorobenzoyl chlorideinstead of 2-fluorobenzoyl chloride, and then the dimer of diketone,oxime and oxime ester are prepared the same procedure as 13.b, 13.c and13.d respectively. The product is composed of an isomeric mixture, andthe structure is confirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]: 1.47(t), 1.52 (t), 2.10 (s), 2.12 (s), 2.34 (s), 3.38 (t), 4.36-4.66 (m),6.90-6.98 (m), 7.04-7.12 (m), 7.14-7.48 (m), 7.50 (s), 7.60 (d), 7.72(br), 8.01 (s), 8.04 (br), 8.28 (br), 8.52 (br).

EXAMPLE 16[[9-[2-[2-[2-[3-[N-acetoxy-C-(o-tolyl)carbonimidoyl]-6-(2,4,6-trimethylbenzoyl)carbazol-9-yl]ethoxy]ethoxy]ethyl]-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]-(o-tolyl)methylene]aminoacetate 16.ao-Tolyl-[6-(2,4,6-trimethylbenzoyl)-9H-carbazol-3-yl]methanone

To 9-benzyl-9H-carbazole (2.50 g; 9.72 mmol) in CH₂Cl₂ (50 mL) are added2,4,6-trimethylbenzoyl chloride (1.86 g; 10.2 mmol) and AlCl₃ (1.48 g;11.1 mmol) at 0° C. After stirring for 2 hours, AlCl₃ (1.55 g; 11.6mmol) is added and o-toluoyl chloride (1.58 g; 10.2 mmol) is addeddropwise, and then the mixture is stirred at room temperature overnight.To the mixture AlCl₃ (1.51 g; 11.3 mmol) is added, and the reactionmixture is stirred for 1 hour at 50° C. The reaction mixture is pouredinto ice-water, and the crude product is extracted twice with CH₂Cl₂.The combined organic layer is washed with water and brine, dried overMgSO₄. After CH₂Cl₂ is removed by concentration, the crude product ispurified by column chromatography on silica gel eluting with CH₂Cl₂ toobtain a white solid (2.23 g, 53%). The structure is confirmed by ¹H-NMRspectrum (CDCl₃). δ [ppm]: 2.00 (s), 2.22 (s), 2.31 (s), 6.96 (s), 7.25(t), 7.31 (d), 7.36 (d), 7.41 (t), 7.43 (t), 7.45 (t), 7.61 (t), 7.63(d), 7.73 (br), 7.78 (d), 7.79 (d), 8 54 (s), 8.55 (s).

16.b[9-[2-[2-[2-[3-(2-methylbenzoyl)-6-(2,4,6-trimethylbenzoyl)carbazol-9-yl]ethoxy]-ethoxy]ethyl]-6-(2,4,6-trimethylbenzovI)carbazol-3-yl]-(o-tolypmethanone

To o-Tolyl-[6-(2,4,6-trimethylbenzoyl)-9H-carbazol-3-yl]methanone (1.62g; 3.76 mmol) in DMA (20 mL) are added triethylene glycolbis(p-toluenesulfonate) (0.90 g; 2.0 mmol) and potassium parbonate (1.11g; 8.39 mmol). After stirring overnight at room temperature, thereaction mixture is poured into ice-water, and the crude product isextracted twice with AcOEt. The combined organic layer is washed withwater and brine, dried over MgSO₄. After AcOEt is removed byconcentration, the crude product is purified by column chromatography onsilica gel eluting with CH₂Cl₂ to obtain a white solid (1.60 g, 87%).The structure is confirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]: 2.01(s), 2.24 (s), 2.33 (s), 3.33 (s), 3.72 (t), 4.37 (t), 6.92 (s),7.16-7.44 (m), 7.86-8.04 (m), 8.50 (s), 8.53 (s).

16.c[6-[N-hydroxy-C-(o-tolyl)carbonimidoyl]-9-[2-[2-[2-[3-[N-hydroxy-C-(o-tolyl)carbonimidoyl]-6-(2,4,6-trimethylbenzoyl)carbazol-9-yl]ethoxy]ethoxy]ethyl]carbazol-3-yl]-(2,4,6-trimethylphenyl)methanone

To[9-[2-[2-[2-[3-(2-methylbenzoyl)-6-(2,4,6-trimethylbenzoyl)carbazol-9-yl]ethoxy]ethoxy]ethyl]-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]-(o-tolyl)methanone(1.50 g; 1.53 mmol) in pyridine (10 mL) is added hydroxylammoniumchloride (7.32 g; 12.0 mmol) at 120° C., and then the mixture is stirredat 120° C. overnight. After it is cooled at room temperature, thereaction mixture is poured into water, and the crude product isextracted twice with AcOEt (ethyl acetate). The combined organic layeris washed with water and brine and dried over MgSO₄. After AcOEt isremoved by concentration, the crude product is purified by columnchromatography on silica gel eluting with a mixed solvent of CH₂Cl₂ andAcOEt (5:1) to obtain a white solid (0.50 g, 33%). The structure isconfirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]: 2.07 (s), 2.21 (s), 2.35(s), 3.33 (s), 3.68 (t), 4.32 (t), 6.90 (s), 7.15 (d), 7.26-7.40 (m),7.69 (br), 7.87 (br), 8.07 (s), 8.53 (br).

16.d[[9-[2-[2-[2-[3-[N-acetoxy-C-(o-tolyl)carbonimidoyl]-6-(2,4,6-trimethylbenzoyl)-carbazol-9-yl]ethoxy]ethoxy]ethyl]-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]-(o-tolyl)methylene]aminoacetate

To[6-[N-hydroxy-C-(o-tolyl)carbonimidoyl]-9-[2-[2-[2-[3-[N-hydroxy-C-(o-tolyl)carbonimidoyl]-6-(2,4,6-trimethylbenzoyl)carbazol-9-yl]ethoxy]ethoxy]ethyl]carbazol-3-yl]-(2,4,6-trimethylphenyl)methanone(0.50 g; 0.50 mmol) in THF (5 mL) are added triethylamine (0.20 g; 2.0mmol) and acetyl chloride (0.15 g; 1.9 mmol) at 0° C. Then the mixtureis stirred at 0° C. for 1.5 hours. The reaction mixture is poured intoice-water, and the crude product is extracted with AcOEt. The combinedorganic layer is washed with H₂O and brine, dried over MgSO₄, andconcentrated. The crude product is purified by column chromatography onsilica gel eluting AcOEt to obtain a white solid (0.36 g, 67%). Thestructure is confirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]: 2.09 (s),2.15 (s), 2.17 (s), 2.35 (s), 3.31 (s), 3.69 (t), 4.32 (t), 6.91 (s),7.09 (d), 7.26-7.41 (m), 7.66 (br), 7.96 (br), 8.31 (br), 8.49 (br).

EXAMPLE 17[[6-[2-[2-[2-[2-[2-[6-[N-acetoxy-C-(o-tolyl)carbonimidoyl]-9-ethyl-carbazole-3-carbonyl]-3-ethoxy-phenoxy]ethoxy]ethoxy]ethoxy]-6-ethoxy-benzoyl]-9-ethyl-carbazol-3-yl]-(o-tolyl)methylene]aminoacetate 17.a ethyl2-ethoxy-6-[2-[2-[2-(3-ethoxy-2-ethoxycarbonyl-phenoxy)ethoxy]-ethoxy]ethoxy]benzoate

To ethyl 6-ethoxy-2-hydroxybenzoate (5.00 g; 23.8 mmol) in DMA (50 mL)are added triethylene glycol bis(p-toluenesulfonate) (5.48 g; 12.0 mmol)and potassium parbonate (9.86 g; 71.4 mmol). After stirring at 80° C.for 3 hours, the reaction mixture is poured into water, and the crudeproduct is extracted twice with AcOEt. The combined organic layer iswashed with water and brine, dried over MgSO₄. After AcOEt is removed byconcentration and dried under vacuo, a white solid is obtained (2.62 g,34%). The structure is confirmed by ¹H-NMR spectrum (CDCl₃). δ[ppm]:1.30-1.39 (m), 3.68 (s), 3.81 (t), 4.04 (q), 4.14 (t), 4.36 (q),6.53 (d), 7.22 (t)

17.b2-[2-[2-[2-(2-carboxy-3-ethoxy-phenoxy)ethoxy]ethoxy]ethoxy]-6-ethoxy-benzoicacid

To ethyl2-ethoxy-6-[2-[2-[2-(3-ethoxy-2-ethoxycarbonyl-phenoxy)ethoxy]ethoxy]ethoxy]benzoate(2.60 g; 4.89 mmol) in a mixed solvent of methanol (30 mL) and H₂O (60mL) is added sodium hydroxide (4.08 g; 102 mmol). After stirring at 100°C. overnight, the reaction mixture is cooled at room temperature. Themixture is acidified with concentrated hydrochloric acid to pH=3.0 andthe crude product is extracted twice with AcOEt. The combined organiclayer is washed with water and brine, dried over MgSO₄. After AcOEt isremoved by concentration, the crude product is purified by columnchromatography on silica gel eluting with AcOEt to obtain a white solid(0.83 g, 35%). The structure is confirmed by ¹H-NMR spectrum (CDCl₃). δ[ppm]: 1.44 (t), 3.88 (s), 3.91 (t), 4.09-4.20 (m), 6.53 (d), 6.59 (d),7.28 (t).

17.c[6-[2-ethoxy-6-[2-[2-[2-[3-ethoxy-2-[9-ethyl-6-(2-methylbenzoyl)carbazole-3-carbonyl]phenoxy]ethoxy]ethoxy]ethoxy]benzoyl]-9-ethyl-carbazol-3-yl]-(o-tolyl)methanone

To2-[2-[2-[2-(2-carboxy-3-ethoxy-phenoxy)ethoxy]ethoxy]ethoxy]-6-ethoxy-benzoicacid (0.83 g; 1.7 mmol) in CH₂Cl₂ (10 mL) are added oxalyl chloride(0.68 g; 5.36 mmol) and 1 drop o DMF. After stirring for 2 hours, CH₂Cl₂is removed by concentration, and the crude product is dried under vacuo.To 9-ethyl-9H-carbazol (0.68 g, 3.5 mmol) in CH₂Cl₂ are added AlCl₃(0.51 g; 3.8 mmol) and o-toluoyl chloride (0.56 g; 3.6 mmol) at 0° C.After stirring for 1 hour, AlCl₃ (0.58 g; 4.3 mmol) and the acidchloride prepared above are added at 0° C., and then the mixture isstirred at room temperature for 3 hours. The reaction mixture is pouredinto ice-water, and the crude product is extracted twice with CH₂Cl₂.The combined organic layer is washed with water and brine, dried overMgSO₄. After CH₂Cl₂ is removed by concentration, the crude product ispurified by column chromatography on silica gel eluting with a mixedsolvent of CH₂Cl₂ and AcOEt (5:1) to obtain a white solid (1.04 g, 56%).The structure is confirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]: 1.13(t), 1.43 (t), 2.31 (s), 2.93 (s), 3.30 (t), 3.88 (t), 4.00 (q), 4.35(q), 6.54 (d), 6.63 (d), 7.24-7.44 (m), 7.94 (d), 7.97 (d), 8.53 (s).

17.d[2-ethoxy-6-[2-[2-[2-[3-ethoxy-2-[9-ethyl-6-[N-hydroxy-C-(o-tolyl)carbonimidoyl]carbazole-3-carbonyl]phenoxy]ethoxy]ethoxy]ethoxy]phenyl]-[9-ethyl-6-[N-hydroxy-C-(o-tolyl)carbonimidoyl]carbazol-3-yl]methanone

To[6-[2-ethoxy-6-[2-[2-[2-[3-ethoxy-2-[9-ethyl-6-(2-methylbenzoyl)carbazole-3-carbonyl]phenoxy]ethoxy]ethoxy]ethoxy]benzoyl]-9-ethyl-carbazol-3-yl]-(o-tolyl)methanone(1.03 g; 0.935 mmol) in pyridine (10 mL) is added hydroxylammoniumchloride (0.41 g; 5.8 mmol) at 120° C., and then the mixture is stirredat 120° C. overnight. After it is cooled at room temperature, thereaction mixture is poured into water, and the crude product isextracted twice with AcOEt (ethyl acetate). The combined organic layeris washed with water and brine and dried over MgSO₄. After AcOEt isremoved by concentration, the crude product is purified by columnchromatography on silica gel eluting with a mixed solvent of CH₂Cl₂ andAcOEt (3:1) to obtain a white solid (0.45 g, 44%). The structure isconfirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]: 1.12 (t), 1.37 (t), 2.22(s), 2.92 (s), 3.29 (t), 3.88 (t), 3.97 (q), 4.27 (q), 6.53 (d), 6.61(d), 7.17 (d), 7.24-7.40 (m), 7.58 (d), 7.88 (d), 8.16 (s), 8.54 (s).

17.e[[6-[2-[2-[2-[2-[2-[6-[N-acetoxy-C-(o-tolyl)carbonimidoyl]-9-ethyl-carbazole-3-carbonyl]-3-ethoxy-phenoxy]ethoxy]ethoxy]ethoxy]-6-ethoxy-benzoyl]-9-ethyl-carbazol-3-yl]-(o-tolyl)methylene]aminoacetate

To[2-ethoxy-6-[2-[2-[2-[3-ethoxy-2-[9-ethyl-6-[N-hydroxy-C-(o-tolyl)carbonimidoyl]carbazole-3-carbonyl]phenoxy]ethoxy]ethoxy]ethoxy]phenyl]-[9-ethyl-6-[N-hydroxy-C-(o-tolyl)carbonimidoyl]carbazol-3-yl]methanone(0.42 g; 0.38 mmol) in THF (10 mL) are added triethylamine (0.12 g; 1.2mmol) and acetyl chloride (0.15 g; 1.9 mmol) at 0° C. Then the mixtureis stirred at 0° C. for 2 hours. The reaction mixture is poured intoice-water, and the crude product is extracted with AcOEt. The combinedorganic layer is washed with H₂O and brine, dried over MgSO₄, andconcentrated. The crude product is purified by column chromatography onsilica gel eluting AcOEt to obtain a white solid (0.38 g, 84%). Thestructure is confirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]: 1.13 (t),1.39 (t), 2.04 (s), 2.17 (s), 2.92 (s), 3.30 (t), 3.88 (t), 3.98 (q),4.30 (q), 6.53 (d), 6.62 (d), 7.11 (d), 7.26-7.42 (m), 7.70 (d), 7.92(d), 8.27 (s), 8.52 (s).

EXAMPLE 18[[6-[2-[2-[2-[2-[[1-[6-[N-acetoxy-C-(o-tolyl)carbonimidoyl]-9-(2-ethylhexyl)-carbazole-3-carbonyl]-2-naphthyl]oxy]ethoxy]ethoxy]ethoxy]naphthalene-1-carbonyl]-9-(2-ethylhexyl)carbazol-3-yl]-(o-tolyl)methylene]aminoacetate

The corresponding dimer intermediate of the diketone is preparedaccording to the procedure as disclosed in example 17.c with thecorresponding diketone, and then the oxime and oxime ester are preparedaccording to the same procedure as 17.d and 17.e respectively.

The structure is confirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]: 0.82(t), 0.85 (t), 1.14-1.40 (m), 1.85 (s), 1.95 (m), 2.04 (s), 3.13 (s),3.39 (t), 4.06 (t), 4.10 (d), 7.10 (d), 7.26-7.42 (m), 7.53 (d), 7.74(d), 7.82 (d), 7.89 (d), 7.90 (d), 8.19 (s), 8.56 (s).

EXAMPLE 19[[2-[6-[2-[N-acetoxy-C-[6-(2-ethoxynaphthalene-1-carbonyl)-9-(2-ethyl-hexyl)carbazol-3-yl]carbonimidoyl]phenoxy]hexoxy]phenyl]-[6-(2-ethoxynaphthalene-1-carbonyl)-9-(2-ethylhexyl)carbazol-3-yl]methylene]aminoacetate

The corresponding dimer intermediate of the diketone is preparedaccording to the procedure as disclosed in example 13.b with thecorresponding diketone, and then the oxime and oxime ester are preparedaccording to the same procedure as 13.c and 13.d respectively.

The structure is confirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]: 0.82(t), 0.85 (t), 1.09 (t), 1.22-1.40 (m), 1.95 (m), 2.05 (s), 3.63 (t),4.08 (t), 4.13 (d), 6.85 (d), 7.04 (t), 7.11 (d), 7.26-7.42 (m), 7.54(d), 7.73 (d), 7.84 (d), 7.94 (d), 7.95 (d), 8.18 (s), 8.57 (s).

EXAMPLE 20[[9-[2-[2-[2-[3-[N-acetoxy-C-(2-methoxyphenyl)carbonimidoyl]-6-(2-ethoxynaphthalene-1-carbonyl)carbazol-9-yl]ethoxy]ethoxy]ethyl]-6-(2-ethoxynaphthalene-1-carbonyl)carbazol-3-yl]-(2-methoxyphenyl)methylene]aminoacetate

The corresponding dimer intermediate of the diketone is preparedaccording to the procedure as disclosed in example 16.b with thecorresponding diketone, and then the oxime and oxime ester are preparedaccording to the same procedure as 16.c and 16.d respectively.

The structure is confirmed by ¹H-NMR spectrum (CDCl₃). δ [ppm]: 1.10(t), 2.05 (s), 3.25 (s), 3.62 (t), 3.70 (s), 4.09 (q), 4.26 (t), 7.02(d), 7.03 (t), 7.08 (d), 7.26-7.34 (m), 7.46 (t), 7.49 (d), 7.76 (d),7.80 (d), 7.88 (d), 7.92 (d), 8.20 (s), 8.57 (s).

APPLICATION EXAMPLES Example A1 Sensitivity Tests

A photocurable composition for a sensitivity test is prepared by mixingthe following components:

11.0 parts by weight of REGAL ® 400 pigment black (provided by CABOT),11.0 parts by weight of EFKA ® 4046, dispersant for pigment provided byBASF), 10.3 parts by weight of Ripoxy ® SPC1000, alkaline solublepoylmer (provided by SHOWA DENKO), 3.6 parts by weight ofdipentaerythritol penta-/hexa-acrylate ((DPHA), provided bySIGMA-ALDRICH) 1.0 parts by weight of photoinitiator 48.5 parts byweight of propylene glycol monomethyl ether acetate (PGMEA) 15.6 partsby weight of cyclohexanone

All operations are carried out under yellow light. The compositions areapplied to a glass plate using a spincoater. The solvent is removed byheating at 80° C. for 10 minutes in a convection oven. The thickness ofthe dry film is approximately 1.2 μm. A stepwedge pattern mask with 9linear steps and 9 logarithmic steps of different optical density(Edumund Optics, EIA GrayScale Pattern Slide) is placed on the resistdirectly. Exposure is carried out using a 250 W super high pressuremercury lamp (USH-IO, USH-250BY) at a distance of 15 cm. A totalexposure dose measured by an optical power meter (ORC UV Light MeasureModel UV-M02 with UV-35 detector) on the glass filter is 500 mJ/cm².After exposure, the exposed film is developed with an alkaline solution(5% aqueous solution of DL-A4, YOKOHAMA OILS & FATS) for 10 secondsafter break time at 28° C. by using a spray type developer (AD-1200,MIKASA). Break time is the development time of the unexposed region. Thenecessary UV dose for full curing (i.e. the pattern is not dissolvedwith the alkaline solution) is calculated from the residual thickness ofeach step after development. The smaller the value of the dose, the moresensitive is the tested initiator. The results are listed in Table 2.

TABLE 2 photoinitiator necessary UV dose of example for full curing 1 39mJ/cm² 2 32 mJ/cm² 3 42 mJ/cm² 4 37 mJ/cm² 6 35 mJ/cm² 7 37 mJ/cm² 8 22mJ/cm² 9 39 mJ/cm² 10 32 mJ/cm² 11 33 mJ/cm² 12 28 mJ/cm² 13 15 mJ/cm²14 15 mJ/cm² 15 29 mJ/cm² 16 18 mJ/cm² 17 19 mJ/cm² 18 22 mJ/cm² 19 23mJ/cm² 20 20 mJ/cm²

1. Compounds of the formula I, II, III, IV or V

wherein Z is

or C₄-C₂₀heteroaroyl which is unsubstituted or substituted by one ormore identical or different R₁₀; Z₁ independently of each other are NO₂,C₇-C₂₀aroyl or C₄-C₂₀heteroaroyl, where C₇-C₂₀aroyl or C₄-C₂₀heteroaroylis unsubstituted or substituted by one or more identical or differentR₁₀; provided that in formula III at least one Z₁ is other than NO₂; Z₂is C₇-C₂₀aroyl or C₄-C₂₀heteroaroyl, where C₇-C₁₈aroyl orC₄-C₂₀heteroaroyl are unsubstituted or substituted by one or moreidentical or different R₁₀; or Z₂ is NO₂; R₁, R₂, R₃, R₄, R₅ and R₆independently of each other are hydrogen, halogen, OR₁₆, SR₁₇, NR₁₈R₁₉,or C₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, OR₁₆, COOR₁₆, CONR₁₈R₁₉ or NR₁₈R₁₉; or R₁, R₂, R₃, R₄, R₅ andR₆ independently of each other are C₆-C₂₀aryl, or C₄-C₂₀heteroaryl, eachof which is unsubstituted or substituted by one or more C₁-C₆alkyl,C₁-C₄haloalkyl or halogen; R₉, R₁₀, R₁₁, R₁₂ and R₁₃ independently ofeach other are hydrogen, halogen, OR₁₆, SR₁₇, NR₁₈R₁₉, CN, NO₂ orC₂-C₂₀alkyl which is interrupted by one or more O, S or NR₂₁, whereinthe interrupted C₂-C₂₀alkyl is unsubstituted or substituted by one ormore halogen, OR₁₆, COOR₁₆, SR₁₇, CONR₁₈R₁₉, C₆-C₂₀aryl,C₃-C₂₀heteroaryl or C₃-C₂₀cycloalkyl, C₃-C₂₀cycloalkyl interrupted byone or more O, S, NR₂₁; or R₉, R₁₀, R₁₁, R₁₂ and R₁₃ independently ofeach other are C₁-C₂₀alkyl which is unsubstituted or substituted by oneor more halogen, OR₁₆, SR₁₇, COOR₁₆, CONR₁₈R₁₉, NR₁₈R₁₉, phenyl,C₃-C₈-cycloalkyl, C₃-C₂₀heteroaryl or M; provided that R₉ and R₁₃ areneither hydrogen nor fluorine; R₁₄ is C₆-C₂₀aryl or C₃-C₂₀heteroaryleach of which is unsubstituted or substituted by one or more phenyl,halogen, C₁-C₄haloalkyl, CN, NO₂, OR₁₆, SR₁₇, NR₁₈R₁₉,PO(OC_(k)H_(2k+1))₂, SO—C₁-C₁₀alkyl, SO₂—C₁-C₁₀alkyl, M,

or by C₂-C₂₀alkyl which is interrupted by one or more O, CO, S, C(O)O,OC(O), phenylene, naphthylene or by NR₂₁, or each of which C₆-C₂₀aryl orC₃-C₂₀heteroaryl is substituted by one or more C₁-C₂₀alkyl which isunsubstituted or substituted by one or more halogen, COOR₁₆, CONR₁₈R₁₉,phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇, NR₁₈R₁₉ or by M; Q isC₆-C₂₀arylene or C₃-C₂₀heteroarylene each of which is unsubstituted orsubstituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₆, SR₁₇, NR₁₈R₁₉, PO(OC_(k)H_(2k+1))₂, SO—C₁-C₁₀alkyl,SO₂—C₁-C₁₀alkyl, M,

or by C₂-C₂₀alkyl which is interrupted by one or more O, CO, S, C(O)O,OC(O), phenylene, naphthylene or by NR₂₁, or each of which C₆-C₂₀aryleneor C₃-C₂₀heteroarylene is substituted by one or more C₁-C₂₀alkyl whichis unsubstituted or substituted by one or more halogen, COOR₁₆,CONR₁₈R₁₉, phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl,C₆-C₂₀aryloxycarbonyl, C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇, NR₁₈R₁₉or by M; Q₁ is a direct bond, C₁-C₂₀alkylene, C₁-C₂₀alkenylene, whichC₁-C₂₀alkylene OR C₁-C₂₀alkenylene are unsubstituted or substituted byone or more halogen, OR₁₆, COOR₁₆, NR₁₈R₁₉, C₁-C₂₀heteroaryl CONR₁₈R₁₉,

phenyl or by phenyl substituted by halogen, C₁-C₂₀alkyl, C₁-C₄haloalkyl,OR₁₆, SR₁₇, or NR₁₈R₁₉; or Q₁ is C₃-C₁₀cycloalkylene orC₃-C₁₀cycloalkenylene, both of which optionally are interrupted by O, COor NR₂₁; or Q₁ is C₂-C₂₀alkylene interrupted by one or more O orC₂-C₂₀alkenylene interrupted by one or more O, which interruptedC₂-C₂₀alkylene or C₂-C₂₀alkenylene is unsubstituted or substituted byone or more halogen, OR₁₆, COOR₁₆, NR₁₈R₁₉, C₁-C₂₀heteroaryl CONR₁₈R₁₉,

phenyl or by phenyl substituted by halogen, C₁-C₂₀alkyl, C₁-C₄haloalkyl,OR₁₆, SR₁₇, or NR₁₈R₁₉; or Q₁ is phenylene, naphthylene, coumarinyleneor C₁-C₂₀heteroarylene, each of which is unsubstituted or substituted byone or more C₁-C₁₂alkyl, phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂, OR₁₆,SR₁₇, NR₁₈R₁₉ or by C₃-C₁₀cycloalkyl which optionally is interrupted byO, CO or NR₂₁; or Q₁ is phenylene-O* or naphthylene-O*, each of which isunsubstituted or substituted by one or more C₁-C₆alkyl, halogen, phenyl,OR₁₆, SR₁₇, or NR₁₈R₁₉; or Q₁ is C₁-C₂₀alkylene-CO* or phenylene-CO*which is unsubstituted or substituted by by one or more C₁-C₆alkyl,halogen, phenyl, OR₁₆, SR₁₇, or NR₁₈R₁₉; or Q₁ is C₁-C₂₀alkylene-O—CO*which is optionally interrupted by one or more O and which interruptedor uninterrupted C₁-C₂₀alkylene-O—CO* is unsubstituted or substituted byone or more OH; or Q₁ is phenylene-O—CO* which is unsubstituted orsubstituted by one or more C₁-C₆alkyl, C₁-C₄haloalkyl, halogen, phenyl,OR₁₆, SR₁₇, or NR₁₈R₁₉; or Q₁ is

p is an integer 1 or 2; where the asterix in the definitions for Q₁denotes the bond to L; Q₂ is

where the double asterix denotes the bond to the carbazyl group andwherein the naphthyleneoyl or phenyleneoyl is unsubstituted orsubstituted by one or more idenical or different R₁₀; Q₃ is phenylene,naphthylene or C₃-C₁₂heteroarylene, all of which are substituted by

M is

G is NO₂ or —COR₂₈; L is C₁-C₂₀alkylene, C₂-C₁₂alkenylene,O-phenylene-O, O-naphthylene-O, S—C₁-C₂₀alkylene-S, S-phenylene-S,S-naphthylene-S, C₂-C₂₀alkylene which is interrupted by one or moregroups selected from the group consisting of O, S, CO, (CO)O, O(CO),phenylene and naphthylene, or L is O—C₁-C₂₀alkylene-O,O—C₂-C₂₀alkylene-O which is interrupted by one or more groups selectedfrom the group consisting of O, S, CO, (CO)O, O(CO), phenylene andnaphthylene, or L is S—C₂-C₂₀alkylene-S which is interrupted by one ormore groups selected from the group consisting of O, S, CO, (CO)O,O(CO), phenylene and naphthylene, wherein all radicals L as defined areunsubstituted or substituted by one or more halogen; R″₁₄ is C₁-C₂₀alkylwhich is unsubstituted or substituted by phenyl or by phenyl which issubstituted by one or more halogen, C₁-C₂₀alkyl, C₁-C₄haloalkyl, OR₁₆,SR₁₇ or by NR₁₈R₁₉; or R″₁₄ is C₂-C₂₀alkyl which is interrupted by oneor more O, CO, S, C(O)O, OC(O), phenylene, naphthylene or NR₂₁, whereinthe interrupted C₂-C₂₀alkyl is unsubstituted or substituted by one ormore halogen, OR₁₆, COOR₁₆, CONR₁₈R₁₉, phenyl or by phenyl which issubstituted by OR₁₆, SR₁₇ or NR₁₈R₁₉; or R″₁₄ is CN, CONR₁₈R₁₉, NO₂,C₁-C₄haloalkyl, S(O)_(m)—C₁-C₆alkyl; S(O)_(m)-phenyl which isunsubstituted or substituted by C₁-C₁₂alkyl or SO₂—C₁-C₆alkyl; or R″₁₄is SO₂O-phenyl which is unsubstituted or substituted by C₁-C₁₂alkyl; oris diphenyl phosphinoyl or di-(C₁-C₄alkoxy)-phosphinoyl; or R″₁₄ isC₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstituted orsubstituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₆, SR₁₇, NR₁₈R₁₉, PO(OC_(k)H_(2k+1))₂, SO—C₁-C₁₀alkyl,SO₂—C₁-C₁₀alkyl, or by C₂-C₂₀alkyl which is interrupted by one or moreO, CO, S, C(O)O, OC(O), phenylene, naphthylene or by NR₂₁, or each ofwhich is substituted by one or more C₁-C₂₀alkyl which is unsubstitutedor substituted by one or more halogen, COOR₁₆, CONR₁₈R₁₉, phenyl,C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇ or by NR₁₈R₁₉; R₁₅ is hydrogen,C₃-C₈cycloalkyl, C₂-C₅alkenyl, C₁-C₂₀alkoxy or C₁-C₂₀alkyl which isunsubstituted or substituted by one or more halogen, phenyl,C₁-C₂₀alkylphenyl or CN; or R₁₅ is phenyl or naphthyl each of which isunsubstituted or substituted by one or more C₁-C₆alkyl, C₁-C₄haloalkyl,halogen, CN, OR₁₆, SR₁₇ or NR₁₈R₁₉; or R₁₅ is C₃-C₂₀heteroaryl,benzyloxy or phenoxy, each of is unsubstituted or substituted by one ormore C₁-C₆alkyl, C₁-C₄haloalkyl or halogen; k is an integer 1-10; m isan integer 1 or 2; R′₁₄ has one of the meanings as given for R₁₄ or isC₁-C₂₀alkyl; R′₁₅ has one of the meanings as given for R₁₅; X₁ is O, CO,S or a direct bond; X₂ is O, S, SO or SO₂; X₃ is O, S or NR′₂₀; R₁₆ ishydrogen, phenyl-C₁-C₃alkyl, C₁-C₂₀alkyl, which is unsubstituted orsubstituted by one or more halogen, OH, SH, CN, C₃-C₆alkenoxy,O(C₁-C₄alkyl), OCH₂CH₂CN, OCH₂CH₂(CO)O(C₁-C₄alkyl), O(CO)—(C₁-C₄alkyl),O(CO)—(C₂-C₄)alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C₁-C₄alkyl),C₃-C₂₀cycloalkyl, SO₂—(C₁-C₄haloalkyl), O(C₁-C₄haloalkyl),O(C₁-C₂₀arylene)-M, or by C₃-C₂₀cycloalkyl which is interrupted by oneor more O; or R₁₆ is C₂-C₂₀alkyl which is interrupted by one or more O,S or NR₂₁, which interrupted C₂-C₂₀alkyl is unsubstituted or substitutedby O—C₆-C₂₀arylene-M, in which O—C₆-C₂₀arylene-M, the arylene isunsubstituted or substituted by one or more C₁-C₆alkyl or O(C₁-C₆alkyl);or R₁₆ is (CH₂CH₂O)_(n+1)H, (CH₂CH₂O)(CO)—(C₁-C₈alkyl), C₁-C₈alkanoyl,C₂-C₁₂alkenyl, C₃-C₆alkenoyl, or C₃-C₂₀cycloalkyl which is uninterruptedor interrupted by one or more O, S, CO or NR₂₁; or R₁₆ isC₁-C₈alkyl-C₃-C₁₀cycloalkyl which is uninterrupted or interrupted by oneor more O; or R₁₆ is benzoyl which is unsubstituted or substituted byone or more C₁-C₆alkyl, halogen, OH, or C₁-C₃alkoxy; or R₁₆ is phenyl,naphthyl or C₃-C₂₀heteroaryl, each of which is unsubstituted orsubstituted by one or more halogen, OH, C₁-C₁₂alkyl, C₁-C₁₂alkoxy, CN,NO₂, phenyl-C₁-C₃alkyloxy, phenoxy, C₁-C₁₂alkylsulfanyl, phenylsulfanyl,N(C₁-C₁₂alkyl)₂, diphenylamino or

n is 1-20; R₁₇ is hydrogen, C₂-C₁₂alkenyl, C₃-C₂₀cycloalkyl orphenyl-C₁-C₃alkyl, wherein the C₂-C₁₂alkenyl, C₃-C₂₀cycloalkyl orphenyl-C₁-C₃alkyl is uninterrupted or interrupted by one or more O, S,CO or NR₂₁; or R₁₇ is C₁-C₂₀alkyl which is unsubstituted or substitutedby one or more OH, SH, CN, C₃-C₆alkenoxy, OCH₂CH₂CN,OCH₂CH₂(CO)O(C₁-C₄alkyl), O(CO)—(C₂-C₄)alkenyl, O(CO)—(C₁-C₄alkyl),O(CO)-phenyl, COOR₁₆ or S—C₆-C₂₀arylene-M; or R₁₇ is C₁-C₂₀alkyl whichis unsubstituted or substituted by one or more OH, SH, CN,C₃-C₆alkenoxy, OCH₂CH₂CN, OCH₂CH₂(CO)O(C₁-C₄alkyl),O(CO)—(C₂-C₄)alkenyl, O(CO)—(C₁-C₄alkyl), O(CO)-phenyl or COOR₁₆; or R₁₇is C₂-C₂₀alkyl which is interrupted by one or more O, S, CO or NR₂₁,which interrupted C₂-C₂₀alkyl is unsubstituted or substituted byS—C₆-C₂₀arylene- M; or R₁₇ is (CH₂CH₂O)_(n)H,(CH₂CH₂O)_(n)(CO)—(C₁-C₈alkyl), C₂-C₈alkanoyl or C₃-C₆alkenoyl; or R₁₇is benzoyl which is unsubstituted or substituted by one or moreC₁-C₆alkyl, halogen, OH, C₁-C₄alkoxy or C₁-C₄alkylsulfanyl; or R₁₇ isphenyl, naphthyl or C₃-C₂₀heteroaryl, each of which is unsubstituted orsubstituted by one or more halogen, C₁-C₁₂alkyl, C₁-C₄haloalkyl,C₁-C₁₂alkoxy, CN, NO₂, phenyl-C₁-C₃alkyloxy, phenoxy,C₁-C₁₂alkylsulfanyl, phenylsulfanyl, N(C₁-C₁₂alkyl)₂, diphenylamino,(CO)O(C₁-C₈alkyl), (CO)—C₁-C₈alkyl, (CO)N(C₁-C₈alkyl)₂ or

R₁₈ and R₁₉ independently of each other are hydrogen, C₁-C₂₀alkyl,C₂-C₄hydroxyalkyl, C₂-C₁₀alkoxyalkyl, C₂-C₅alkenyl, C₃-C₂₀cycloalkyl,phenyl-C₁-C₃alkyl, C₁-C₈alkanoyl, C₁-C₈alkanoyloxy, C₃-C₁₂alkenoyl,SO₂—(C₁-C₄haloalkyl) or benzoyl; or R₁₈ and R₁₉ are phenyl, naphthyl orC₃-C₂₀heteroaryl, each of which is unsubstituted or substituted by oneor more halogen, C₁-C₄haloalkyl, C₁-C₂₀alkoxy, C₁-C₁₂alkyl, benzoyl orC₁-C₁₂alkoxy; or R₁₈ and R₁₉ together with the N-atom to which they areattached form a 5- or 6-membered saturated or unsaturated ring which isuninterrupted or is interrupted by O, S, or NR₂₁, and which 5- or6-membered saturated or unsaturated ring is unsubstituted or substitutedby one or more C₁-C₂₀alkyl, C₁-C₂₀alkoxy, ═O, OR₁₆, SR₁₇, NR₃₁R₃₂,COR₄₁, NO₂, halogen, C₁-C₄-haloalkyl, CN, phenyl,

or by C₃-C₂₀cyclalkyl which is uninterrupted or is interrupted by one ormore O, S, CO or NR₂₁; or R₁₈ and R₁₉ together with the N-atom to whichthey are attached form a group

R₂₀ is hydrogen, COR₄₁ or C₁-C₂₀alkyl which is unsubstituted orsubstituted by one or more halogen, OR₁₆, SR₁₇, COOR₁₆, CONR₁₈R₁₉,NR₁₈R₁₉, PO(OC_(k)H_(2k+1))₂ or M; or R₂₀ is C₂-C₂₀alkyl which isinterrupted by one or more O, CO, C(O)O, OC(O) or NR₂₁, wherein theinterrupted C₂-C₂₀alkyl is unsubstituted or substituted by one or morehalogen, OR₁₆, SR₁₇, COOR₁₆, CONR₁₈R₁₉, NR₁₈R₁₉ or M; or R₂₀ isC₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstituted orsubstituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₆, SR₁₇, NR₁₈R₁₉, M, Z,

or by C₁-C₂₀alkyl which is interrupted by one or more O, S or NR₂₁, oreach of which C₆-C₂₀aryl or C₃-C₂₀heteroaryl is substituted by one ormore C₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, COOR₁₆, CONR₁₈R₁₉, phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl,C₆-C₂₀aryloxycarbonyl, C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇ orNR₁₈R₁₉; R′₂₀ is hydrogen, COR₄₁ or C₁-C₂₀alkyl which is unsubstitutedor substituted by one or more halogen, OR₁₆, SR₁₇, COOR₁₆, CONR₁₈R₁₉,NR₁₈R₁₉ or PO(OC_(k)H_(2k+1))₂; or R′₂₀ is C₂-C₂₀alkyl of which isinterrupted by one or more O, CO, C(O)O, OC(O) or NR₂₁, wherein theinterrupted C₂-C₂₀alkyl is unsubstituted or substituted by one or morehalogen, OR₁₆, SR₁₇, COOR₁₆, CONR₁₈R₁₉ or NR₁₈R₁₉; or R′₂₀ is C₆-C₂₀arylor C₃-C₂₀heteroaryl each of which is unsubstituted or substituted by oneor more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂, OR₁₆, SR₁₇, NR₁₈R₁₉,

or by C₁-C₂₀alkyl which is interrupted by one or more O, S or NR₂₁, oreach of which C₆-C₂₀aryl or C₃-C₂₀heteroaryl is substituted by one ormore C₁-C₂₀alkyl which is unsubstituted or substituted by one or morehalogen, COOR₁₆, CONR₁₈R₁₉, phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl,C₆-C₂₀aryloxycarbonyl, C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇ orNR₁₈R₁₉; R₂₁ is hydrogen, C₁-C₂₀alkyl, C₁-C₄haloalkyl or C₂-C₂₀alkylwhich is interrupted by one or more O, CO, C(O)O or OC(CO), or R₂₁ isCOR₄₁, phenyl-C₁-C₄alkyl or C₃-C₈cycloalkyl which is uninterrupted or isinterrupted by one or more O or CO, or R₂₁ is phenyl or naphthyl both ofwhich are unsubstituted or substituted by one or more C₁-C₂₀alkyl,halogen, C₁-C₄haloalkyl, OR₁₆, SR₁₇, NR₁₈R₁₉ or

R₂₂, R₂₃, R₂₄, R₂₅, R₂₆ or R₂₇ independently of each other are hydrogen,COR₄₁, NO₂ or

or one of R₂₂, R₂₃ or R₂₄ and one of R₂₅, R₂₆ or R₂₇ together with X₃and the phenyl rings to which they are attached form a heteroaromaticring system; R₂₈ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which isunsubstituted or substituted by one or more phenyl, halogen,C₁-C₄haloalkyl, CN, NO₂, OR₁₆, SR₁₇, NR₁₈R₁₉ or by C₂-C₂₀alkyl which isinterrupted by one or more O, S or NR₂₁, or each of which C₆-C₂₀aryl orC₃-C₂₀heteroaryl is substituted by one or more C₁-C₂₀alkyl which isunsubstituted or substituted by one or more halogen, COOR₁₆, CONR₁₈R₁₉,phenyl, C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇ or NR₁₈R₁₉; R₂₉ is COOR₁₆,CONR₁₈R₁₉, (CO)R₁₆; or R₂₉ has one of the meanings given for R₁₈ andR₁₉; R₃₀ is COOR₁₆, CONR₁₈R₁₉, (CO)R₁₆; or R₃₀ has one of the meaningsgiven for R₁₆; R₃₁ and R₃₂ independently of each other are hydrogen,C₁-C₂₀alkyl, C₁-C₄haloalkyl, C₃-C₁₀cycloalkyl or phenyl; or R₃₁ and R₃₂together with N-atom to which they are attached form a 5- or 6-memberedsaturated or unsaturated ring, which is uninterrupted or is interruptedby O, S or NR₂₁, and which 5- or 6-membered saturated or unsaturatedring is not condensed or to which 5- or 6-membered saturated orunsaturated ring a benzene ring is condensed; R₃₃, R₃₄, R₃₅, R₃₆, R₃₇,R₃₈, R₃₉ and R₄₀ independently of each other are hydrogen,

NO₂, COR₄₁, C₁-C₂₀alkyl, C₁-C₄haloalkyl, OR₁₆, SR₁₇, NR₁₈R₁₉, halogen,CN, phenyl or C₃-C₂₀cycloalkyl which is uninterrupted or is interruptedby one or more O, S, CO or NR₂₁; or R₃₅ and R₃₆ or R₃₇ and R₃₈ or both,R₃₅ and R₃₆ and R₃₇ and R₃₈ are

R₄₁ is C₆-C₂₀aryl or C₃-C₂₀heteroaryl each of which is unsubstituted orsubstituted by one or more phenyl, halogen, C₁-C₄haloalkyl, CN, NO₂,OR₁₆, SR₁₇, NR₁₈R₁₉ or by C₂-C₂₀alkyl which is interrupted by one ormore O, S or NR₂₁, or each of which C₆-C₂₀aryl or C₃-C₂₀heteroaryl issubstituted by one or more C₁-C₂₀alkyl which is unsubstituted orsubstituted by one or more halogen, COOR₁₆, CONR₁₈R₁₉, phenyl,C₃-C₈cycloalkyl, C₃-C₂₀heteroaryl, C₆-C₂₀aryloxycarbonyl,C₃-C₂₀heteroaryloxycarbonyl, OR₁₆, SR₁₇ or NR₁₈R₁₉; or R₄₁ is

or R₄₁ is hydrogen, OH, C₁-C₂₀alkyl, C₁-C₄haloalkyl, C₂-C₂₀alkyl whichis interrupted by one or more O, CO or NR₂₁, or R₄₁ is C₃-C₂₀cycloalkylwhich is uninterrupted or is interrupted by O, S, CO or NR₂₁; R₄₂ ishydrogen, C₃-C₈cycloalkyl, C₂-C₅alkenyl, C₁-C₂₀alkoxy or is C₁-C₂₀alkylwhich is unsubstituted or substituted by by one or more halogen, phenyl,C₁-C₂₀alkylphenyl or CN; or R₄₂ is phenyl or naphthyl, both of which areunsubstituted or substituted by one or more C₁-C₆alkyl, C₁-C₄haloalkyl,halogen, CN, OR₁₆, SR₁₇ or NR₁₈R₁₉; or R₄₂ is benzyloxy or phenoxy bothof which are unsubstituted or substituted one or more C₁-C₆alkyl,C₁-C₄haloalkyl or halogen.
 2. Compounds of the formula I, II, III or IVaccording to claim 1, wherein Z is

Z₁ is C₇-C₂₀aroyl, which is unsubstituted or substituted by one or moreidentical or different R₁₀; R₁, R₂, R₃, R₄, R₅ and R₆ are hydrogen; R₁₀and R₁₂ are hydrogen; R₁₁ is hydrogen, OR₁₆ or C₁-C₂₀alkyl; R₉ and R₁₃independently of each other are OR₁₆ or C₁-C₂₀alkyl; R₁₄ is C₆-C₂₀arylwhich is unsubstituted or substituted by one or more NO₂, OR₁₆, NR₁₈R₁₉or C₁-C₂₀alkyl which C₁-C₂₀alkyl is unsubstituted or substituted bySR₁₇; Q is C₆-C₂₀arylene; Q₁ is C₁-C₂₀alkylene; Q₂ is

where the double asterix denotes the bond to the carbazyl group; M is

G is —COR₂₈; L is O—C₁-C₂₀alkylene-O, O—C₂-C₂₀alkylene-O which isinterrupted by one or more O; R″₁₄ is C₁-C₂₀alkyl or C₆-C₂₀aryl whichC₆-C₂₀aryl is unsubstituted or substituted by C₁-C₂₀alkyl; R₁₅ isC₁-C₂₀alkyl; R′₁₄ is C₁-C₂₀alkyl; R′₁₅ is C₁-C₂₀alkyl; X₃ together withR₂₄ and R₂₇ and the phenyl rings to which they are attached forms aheteroaromatic ring system; R₁₆ is C₁-C₂₀alkyl, which is unsubstitutedor substituted by one or more halogen, OH, O(C₁-C₄alkyl),O(CO)—(C₁-C₄alkyl) or O(C₁-C₂₀arylene)-M; or R₁₆ is C₂-C₂₀alkyl which isinterrupted by one or more O, which interrupted C₂-C₂₀alkyl issubstituted by O—C₆-C₂₀arylene-M, in which O—C₆-C₂₀arylene-M, thearylene is unsubstituted or substituted by O(C₁-C₆alkyl); or R₁₆ isC₁-C₈alkanoyl; R₁₇ is is C₁-C₂₀alkyl which is unsubstituted orsubstituted by COOR₁₆; R₁₈ and R₁₉ independently of each other areC₁-C₂₀alkyl, or R₁₈ and R₁₉ together with the N-atom to which they areattached form a 5- or 6-membered saturated or unsaturated ring which isuninterrupted or is interrupted by O, or R₁₈ and R₁₉ together with theN-atom to which they are attached form a group

R₂₀ is C₁-C₂₀alkyl or C₂-C₂₀alkyl of which is interrupted by one or moreO, wherein the interrupted C₂-C₂₀alkyl is unsubstituted or substitutedby NR₁₈R₁₉; or R₂₀ is C₆-C₂₀aryl which is substituted by

R₂₂, R₂₃, R₂₅ and R₂₆ are hydrogen, R₂₄ and R₂₇ together with X₃ and thephenyl rings to which they are attached form a heteroaromatic ringsystem; R₂₈ is C₆-C₂₀aryl which is unsubstituted or substituted byC₁-C₂₀alkyl; R₃₃, R₃₅, R₃₆, R₃₇, R₃₈ and R₄₀ independently of each otherare hydrogen; R₃₄ is

R₃₉ is COR₄₁; R₄₁ is C₆-C₂₀aryl which is unsubstituted or substituted byC₁-C₂₀alkyl.
 3. Compounds of the formula I, II, III or IV according toclaim 2, wherein Z₁ is C₇-C₂₀aroyl, which is substituted by R₁₀; R″₁₄ isC₁-C₂₀alkyl or C₆-C₂₀aryl which is substituted by C₁-C₂₀alkyl; R₁₆ isC₁-C₂₀alkyl, which is unsubstituted or substituted by one or morehalogen, OH, O(C₁-C₄alkyl), O(CO)—(C₁-C₄alkyl) or O(C₁-C₂₀arylene)-M; orR₁₆ is C₂-C₂₀alkyl which is interrupted by one or more O, whichinterrupted C₂-C₂₀alkyl is substituted by O—C₆-C₂₀arylene-M, in whichO—C₆-C₂₀arylene-M, the arylene is substituted by O(C₁-C₆alkyl); or R₁₆is C₁-C₈alkanoyl; R₁₇ is is C₁-C₂₀alkyl which is substituted by COOR₁₆;R₁₈ and R₁₉ independently of each other are C₁-C₂₀alkyl, or R₁₈ and R₁₉together with the N-atom to which they are attached form a 6-memberedsaturated ring which is uninterrupted or is interrupted by O, or R₁₈ andR₁₉ together with the N-atom to which they are attached form a group

R₂₀ is C₁-C₂₀alkyl or C₂-C₂₀alkyl of which is interrupted by one or moreO, wherein the interrupted C₂-C₂₀alkyl is substituted by NR₁₈R₁₉; or R₂₀is C₆-C₂₀aryl which is substituted by

R₂₄ and R₂₇ together with X₃ and the phenyl rings to which they areattached form a carbazolyl ring system; R₂₈ is C₆-C₂₀aryl which issubstituted by C₁-C₂₀alkyl; R₄₁ is C₆-C₂₀aryl which is substituted byC₁-C₂₀alkyl.
 4. A photopolymerizable composition comprising (a) at leastone ethylenically unsaturated photopolymerizable compound and (b) asphotoinitiator, at least one compound of the formula I, II, III, IV or Vas defined in claim
 1. 5. A photopolymerizable composition according toclaim 4, wherein the component (a) is a resin obtained by the reactionof a saturated or unsaturated polybasic acid anhydride with a product ofthe reaction of an epoxy resin and an unsaturated monocarboxylic acid.6. A photopolymerizable composition according to claim 4, additionallyto the photoinitiator (b) comprising at least one further photoinitiator(c), and/or other additives (d).
 7. A photopolymerizable compositionaccording to claim 6 as further additive (d) comprising a pigment or amixture of pigments or a mixture of one or more pigments with one ormore dyes.
 8. A photopolymerizable composition according to claim 7 asfurther additive (d) comprising a dispersant or a mixture ofdispersants.
 9. A photopolymerizable composition according to claim 4,comprising 0.05 to 25% by weight of the photoinitiator (b), or thephotoinitiators (b) and (c), based on the composition.
 10. Aphotopolymerizable composition according to claim 4 as further additive(d) comprising a photosensitizer, in particular a compound selected fromthe group consisting of benzophenone, benzophenone derivatives,thioxanthone, thioxanthone derivatives, anthraquinone, anthraquinonederivatives, coumarin and coumarine derivatives.
 11. Aphotopolymerizable composition according to claim 4 additionallycomprising a binder polymer (e), in particular a copolymer ofmethacrylate and methacrylic acid.
 12. A process for the preparation ofa compound of the formula I, II, III, IV or V according to claim 1 byreacting the corresponding oxime compound of formula IA, IIA, IIIA, IVAor VA

wherein Z, Z₁, Z₂, Q, Q₁, Q₂, Q₃, L, R₁, R₂, R₃, R₄, R₅, R₆, R₂₀, andR₁₄ are as defined in claim 1, with an acyl halide of the formula 2 oran anhydride of the formula 3

wherein Hal is a halogen, in particular Cl, and R₁₅ is as defined inclaim 1, in the presence of a base or a mixture of bases.
 13. A processfor the photopolymerization of compounds containing ethylenicallyunsaturated double bonds, which comprises irradiating a compositionaccording to claim 4 with electromagnetic radiation in the range from150 to 600 nm, or with electron beam or with X-rays.
 14. A color filterprepared by providing red, green and blue picture elements andoptionally a black matrix, all comprising a photosensitive resin and apigment on a transparent substrate and providing a transparent electrodeeither on the surface of the substrate or on the surface of the colorfilter layer, wherein said photosensitive resin comprises apolyfunctional acrylate monomer, an organic polymer binder and aphotopolymerization initiator of formula I, II, III, IV or V as definedin claim
 1. 15. Compounds of the IA, IIA, IIIA, IVA or VA

wherein Z, Z₁, Z₂, Q, Q₁, Q₂, Q₃, L, R₁, R₂, R₃, R₄, R₅, R₆, R₂₀, andR₁₄ are as defined in claim
 1. 16. A coated substrate which is coated onat least one surface with a composition according to claim
 4. 17. Aprocess for the photographic production of relief images, in which acoated substrate according to claim 16 is subjected to imagewiseexposure and then the unexposed portions are removed with a developer.18. Use of a compound of the formula I, II, III, IV or V according toclaim 1 for the photopolymerization of a composition comprising at leastone ethylenically unsaturated photopolymerizable compound.
 19. Processaccording to claim 13 for producing pigmented and nonpigmented paintsand varnishes, powder coatings, printing inks, printing plates,adhesives, dental compositions, gel coats, photoresists, forencapsulating electrical and electronic components, for producingmagnetic recording materials, micromechanical parts, waveguides, opticalswitches, plating masks, colour proofing systems, glass fibre cablecoatings, screen printing stencils, three-dimensional objects by meansof stereolithography, image recording materials for holographicrecordings, microelectronic circuits, decolorizing materials,formulations containing microcapsules.